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Sample records for quantitative structure-property relationship

  1. Development of quantitative structure property relationships for poly(arylene ether)s.

    PubMed

    Hamerton, I; Howlin, B J; Larwood, V

    1995-02-01

    The technique of quantitative structure-activity relationships (QSAR) is well accepted by the drug design community. The analogous technique of quantitative structure-property relationships (QSPR) has applications in the field of polymer chemistry. A variety of molecular modeling and molecular orbital techniques was used to find molecular descriptors that could be used to derive an empirical equation to describe the glass transition temperature of two related classes of poly(arylene ether)s. The derived equation was then used to predict the thermal characteristics of another polymer of the same type. PMID:7794828

  2. Quantitative structure property relationship modeling of excipient properties for prediction of formulation characteristics.

    PubMed

    Gaikwad, Vinod L; Bhatia, Neela M; Desai, Sujit A; Bhatia, Manish S

    2016-10-20

    Quantitative structure property relationship (QSPR) is used to relate the excipient descriptors with the formulation properties. A QSPR model is developed by regression analysis of selected descriptors contributing towards the targeted formulation properties. Developed QSPR model is validated by the true external method where it showed good accuracy and precision in predicting the formulation composition as experimental t90% (61.35min) is observed very close to predicted t90% (67.37min). Hence, QSPR approach saves resources by predicting drug release from an unformulated formulation; avoiding repetitive trials in the development of a new formulation and/or optimization of existing one. PMID:27474604

  3. Linear and nonlinear quantitative structure-property relationship modelling of skin permeability.

    PubMed

    Khajeh, A; Modarress, H

    2014-01-01

    In this work, quantitative structure-property relationship (QSPR) models were developed to estimate skin permeability based on theoretically derived molecular descriptors and a diverse set of experimental data. The newly developed method combining modified particle swarm optimization (MPSO) and multiple linear regression (MLR) was used to select important descriptors and develop the linear model using a training set of 225 compounds. The adaptive neuro-fuzzy inference system (ANFIS) was used as an efficient nonlinear method to correlate the selected descriptors with experimental skin permeability data (log Kp). The linear and nonlinear models were assessed by internal and external validation. The obtained models with three descriptors show good predictive ability for the test set, with coefficients of determination for the MPSO-MLR and ANFIS models equal to 0.874 and 0.890, respectively. The QSPR study suggests that hydrophobicity (encoded as log P) is the most important factor in transdermal penetration. PMID:24090175

  4. Interactions of Indole Derivatives with β-Cyclodextrin: A Quantitative Structure-Property Relationship Study

    PubMed Central

    Šoškić, Milan; Porobić, Ivana

    2016-01-01

    Retention factors for 31 indole derivatives, most of them with auxin activity, were determined by high-performance liquid chromatography, using bonded β-cyclodextrin as a stationary phase. A three-parameter QSPR (quantitative structure-property relationship) model, based on physico-chemical and structural descriptors was derived, which accounted for about 98% variations in the retention factors. The model suggests that the indole nucleus occupies the relatively apolar cavity of β-cyclodextrin while the carboxyl group of the indole -3-carboxylic acids makes hydrogen bonds with the hydroxyl groups of β-cyclodextrin. The length and flexibility of the side chain containing carboxyl group strongly affect the binding of these compounds to β-cyclodextrin. Non-acidic derivatives, unlike the indole-3-carboxylic acids, are poorly retained on the column. A reasonably well correlation was found between the retention factors of the indole-3-acetic acids and their relative binding affinities for human serum albumin, a carrier protein in the blood plasma. A less satisfactory correlation was obtained when the retention factors of the indole derivatives were compared with their affinities for auxin-binding protein 1, a plant auxin receptor. PMID:27124734

  5. Interactions of Indole Derivatives with β-Cyclodextrin: A Quantitative Structure-Property Relationship Study.

    PubMed

    Šoškić, Milan; Porobić, Ivana

    2016-01-01

    Retention factors for 31 indole derivatives, most of them with auxin activity, were determined by high-performance liquid chromatography, using bonded β-cyclodextrin as a stationary phase. A three-parameter QSPR (quantitative structure-property relationship) model, based on physico-chemical and structural descriptors was derived, which accounted for about 98% variations in the retention factors. The model suggests that the indole nucleus occupies the relatively apolar cavity of β-cyclodextrin while the carboxyl group of the indole -3-carboxylic acids makes hydrogen bonds with the hydroxyl groups of β-cyclodextrin. The length and flexibility of the side chain containing carboxyl group strongly affect the binding of these compounds to β-cyclodextrin. Non-acidic derivatives, unlike the indole-3-carboxylic acids, are poorly retained on the column. A reasonably well correlation was found between the retention factors of the indole-3-acetic acids and their relative binding affinities for human serum albumin, a carrier protein in the blood plasma. A less satisfactory correlation was obtained when the retention factors of the indole derivatives were compared with their affinities for auxin-binding protein 1, a plant auxin receptor. PMID:27124734

  6. Predicting adsorption of aromatic compounds by carbon nanotubes based on quantitative structure property relationship principles

    NASA Astrophysics Data System (ADS)

    Rahimi-Nasrabadi, Mehdi; Akhoondi, Reza; Pourmortazavi, Seied Mahdi; Ahmadi, Farhad

    2015-11-01

    Quantitative structure property relationship (QSPR) models were developed to predict the adsorption of aromatic compounds by carbon nanotubes (CNTs). Five descriptors chosen by combining self-organizing map and stepwise multiple linear regression (MLR) techniques were used to connect the structure of the studied chemicals with their adsorption descriptor (K∞) using linear and nonlinear modeling techniques. Correlation coefficient (R2) of 0.99 and root-mean square error (RMSE) of 0.29 for multilayered perceptron neural network (MLP-NN) model are signs of the superiority of the developed nonlinear model over MLR model with R2 of 0.93 and RMSE of 0.36. The results of cross-validation test showed the reliability of MLP-NN to predict the K∞ values for the aromatic contaminants. Molar volume and hydrogen bond accepting ability were found to be the factors much influencing the adsorption of the compounds. The developed QSPR, as a neural network based model, could be used to predict the adsorption of organic compounds by CNTs.

  7. Application of quantitative structure-property relationship analysis to estimate the vapor pressure of pesticides.

    PubMed

    Goodarzi, Mohammad; Coelho, Leandro dos Santos; Honarparvar, Bahareh; Ortiz, Erlinda V; Duchowicz, Pablo R

    2016-06-01

    The application of molecular descriptors in describing Quantitative Structure Property Relationships (QSPR) for the estimation of vapor pressure (VP) of pesticides is of ongoing interest. In this study, QSPR models were developed using multiple linear regression (MLR) methods to predict the vapor pressure values of 162 pesticides. Several feature selection methods, namely the replacement method (RM), genetic algorithms (GA), stepwise regression (SR) and forward selection (FS), were used to select the most relevant molecular descriptors from a pool of variables. The optimum subset of molecular descriptors was used to build a QSPR model to estimate the vapor pressures of the selected pesticides. The Replacement Method improved the predictive ability of vapor pressures and was more reliable for the feature selection of these selected pesticides. The results provided satisfactory MLR models that had a satisfactory predictive ability, and will be important for predicting vapor pressure values for compounds with unknown values. This study may open new opportunities for designing and developing new pesticide. PMID:26890190

  8. Quantitative Structure-Property Relationship (QSPR) Modeling of Drug-Loaded Polymeric Micelles via Genetic Function Approximation

    PubMed Central

    Lin, Wenjing; Chen, Quan; Guo, Xindong; Qian, Yu; Zhang, Lijuan

    2015-01-01

    Self-assembled nano-micelles of amphiphilic polymers represent a novel anticancer drug delivery system. However, their full clinical utilization remains challenging because the quantitative structure-property relationship (QSPR) between the polymer structure and the efficacy of micelles as a drug carrier is poorly understood. Here, we developed a series of QSPR models to account for the drug loading capacity of polymeric micelles using the genetic function approximation (GFA) algorithm. These models were further evaluated by internal and external validation and a Y-randomization test in terms of stability and generalization, yielding an optimization model that is applicable to an expanded materials regime. As confirmed by experimental data, the relationship between microstructure and drug loading capacity can be well-simulated, suggesting that our models are readily applicable to the quantitative evaluation of the drug-loading capacity of polymeric micelles. Our work may offer a pathway to the design of formulation experiments. PMID:25780923

  9. Quantitative Structure-Property Relationship Modeling of Electronic Properties of Graphene Using Atomic Radial Distribution Function Scores.

    PubMed

    Fernandez, Michael; Shi, Hongqing; Barnard, Amanda S

    2015-12-28

    The intrinsic relationships between nanoscale features and electronic properties of nanomaterials remain poorly investigated. In this work, electronic properties of 622 computationally optimized graphene structures were mapped to their structures using partial-least-squares regression and radial distributions function (RDF) scores. Quantitative structure-property relationship (QSPR) models were calibrated with 70% of a virtual data set of 622 passivated and nonpassivated graphenes, and we predicted the properties of the remaining 30% of the structures. The analysis of the optimum QSPR models revealed that the most relevant RDF scores appear at interatomic distances in the range of 2.0 to 10.0 Å for the energy of the Fermi level and the electron affinity, while the electronic band gap and the ionization potential correlate to RDF scores in a wider range from 3.0 to 30.0 Å. The predictions were more accurate for the energy of the Fermi level and the ionization potential, with more than 83% of explained data variance, while the electron affinity exhibits a value of ∼80% and the energy of the band gap a lower 70%. QSPR models have tremendous potential to rapidly identify hypothetical nanomaterials with desired electronic properties that could be experimentally prepared in the near future. PMID:26619798

  10. Quantitative structure-property relationship analysis for the retention index of fragrance-like compounds on a polar stationary phase.

    PubMed

    Rojas, Cristian; Duchowicz, Pablo R; Tripaldi, Piercosimo; Pis Diez, Reinaldo

    2015-11-27

    A quantitative structure-property relationship (QSPR) was developed for modeling the retention index of 1184 flavor and fragrance compounds measured using a Carbowax 20M glass capillary gas chromatography column. The 4885 molecular descriptors were calculated using Dragon software, and then were simultaneously analyzed through multivariable linear regression analysis using the replacement method (RM) variable subset selection technique. We proceeded in three steps, the first one by considering all descriptor blocks, the second one by excluding conformational descriptor blocks, and the last one by analyzing only 3D-descriptor families. The models were validated through an external test set of compounds. Cross-validation methods such as leave-one-out and leave-many-out were applied, together with Y-randomization and applicability domain analysis. The developed model was used to estimate the I of a set of 22 molecules. The results clearly suggest that 3D-descriptors do not offer relevant information for modeling the retention index, while a topological index such as the Randić-like index from reciprocal squared distance matrix has a high relevance for this purpose. PMID:26521096

  11. On the Development and Use of Large Chemical Similarity Networks, Informatics Best Practices and Novel Chemical Descriptors towards Materials Quantitative Structure Property Relationships

    ERIC Educational Resources Information Center

    Krein, Michael

    2011-01-01

    After decades of development and use in a variety of application areas, Quantitative Structure Property Relationships (QSPRs) and related descriptor-based statistical learning methods have achieved a level of infamy due to their misuse. The field is rife with past examples of overtrained models, overoptimistic performance assessment, and outright…

  12. Specific catalysis of asparaginyl deamidation by carboxylic acids: kinetic, thermodynamic, and quantitative structure-property relationship analyses.

    PubMed

    Connolly, Brian D; Tran, Benjamin; Moore, Jamie M R; Sharma, Vikas K; Kosky, Andrew

    2014-04-01

    Asparaginyl (Asn) deamidation could lead to altered potency, safety, and/or pharmacokinetics of therapeutic protein drugs. In this study, we investigated the effects of several different carboxylic acids on Asn deamidation rates using an IgG1 monoclonal antibody (mAb1*) and a model hexapeptide (peptide1) with the sequence YGKNGG. Thermodynamic analyses of the kinetics data revealed that higher deamidation rates are associated with predominantly more negative ΔS and, to a lesser extent, more positive ΔH. The observed differences in deamidation rates were attributed to the unique ability of each type of carboxylic acid to stabilize the energetically unfavorable transition-state conformations required for imide formation. Quantitative structure property relationship (QSPR) analysis using kinetic data demonstrated that molecular descriptors encoding for the geometric spatial distribution of atomic properties on various carboxylic acids are effective determinants for the deamidation reaction. Specifically, the number of O-O and O-H atom pairs on carboxyl and hydroxyl groups with interatomic distances of 4-5 Å on a carboxylic acid buffer appears to determine the rate of deamidation. Collectively, the results from structural and thermodynamic analyses indicate that carboxylic acids presumably form multiple hydrogen bonds and charge-charge interactions with the relevant deamidation site and provide alignment between the reactive atoms on the side chain and backbone. We propose that carboxylic acids catalyze deamidation by stabilizing a specific, energetically unfavorable transition-state conformation of l-asparaginyl intermediate II that readily facilitates bond formation between the γ-carbonyl carbon and the deprotonated backbone nitrogen for cyclic imide formation. PMID:24620787

  13. Notes on quantitative structure-properties relationships (QSPR) part 2: the role of the number of atoms as a molecular descriptor.

    PubMed

    Carbó-Dorca, Ramon; Gallegos Saliner, Ana

    2009-10-01

    A previous analysis performed in our laboratory about the polynomial dependency of the atomic quantum self-similarity measures on the atomic number, together with recent publications on quantitative structure-properties relationships (QSPR), based on the number of molecular atoms, published by various authors, have driven us to show here that a simplified form of the fundamental quantum QSPR (QQSPR) equation, permits to theoretically demonstrate the important, but obvious, role of the number of atoms in a molecule, as a possible molecular descriptor. A discussion of the practical use of the number of atoms in QSPR is also given at the end, which also contains a discussion on the role of Ockham's razor in descriptor simplification choices. PMID:19242962

  14. A quantitative structure- property relationship of gas chromatographic/mass spectrometric retention data of 85 volatile organic compounds as air pollutant materials by multivariate methods

    PubMed Central

    2012-01-01

    A quantitative structure-property relationship (QSPR) study is suggested for the prediction of retention times of volatile organic compounds. Various kinds of molecular descriptors were calculated to represent the molecular structure of compounds. Modeling of retention times of these compounds as a function of the theoretically derived descriptors was established by multiple linear regression (MLR) and artificial neural network (ANN). The stepwise regression was used for the selection of the variables which gives the best-fitted models. After variable selection ANN, MLR methods were used with leave-one-out cross validation for building the regression models. The prediction results are in very good agreement with the experimental values. MLR as the linear regression method shows good ability in the prediction of the retention times of the prediction set. This provided a new and effective method for predicting the chromatography retention index for the volatile organic compounds. PMID:22594439

  15. A new quantitative structure-property relationship model to predict bioconcentration factors of polychlorinated biphenyls (PCBs) in fishes using E-state index and topological descriptors.

    PubMed

    de Melo, Eduardo Borges

    2012-01-01

    A quantitative structure-property relationship (QSPR) study for predicting the logarithm of bioconcentration factors (LogBCF) of polychlorinated biphenyls (PCBs) is presented in this work. For this, the descriptors were obtained using only the Simplified Molecular Input Line Entry System (SMILES) strings in the free web server Parameter Client. The model was built using the Partial Least Squares (PLS) regression method. The best model presented five descriptors (one E-state index and four topological descriptors) and a high quality for fit, internal, and external predictions. The leave-N-out (LNO) cross validation and the y-randomization test showed the model is robust and has no shown chance correlation. With a second test set, the model was compared to other models and presented a root mean square error (RMSE) very close to the best model. The mechanistic interpretation was corroborated by other works in the literature and by the descriptors' theory. Thus, the results meet the five Organization for Economic Co-operation and Development (OECD) principles for validation of QSA(P)R models, and it is expected the model can effectively predict the BCF values in fishes of the PCB congeners without highly reliable experimental BCF. PMID:21959189

  16. Notes on quantitative structure-property relationships (QSPR), part 3: density functions origin shift as a source of quantum QSPR algorithms in molecular spaces.

    PubMed

    Carbó-Dorca, Ramon

    2013-04-01

    A general algorithm implementing a useful variant of quantum quantitative structure-property relationships (QQSPR) theory is described. Based on quantum similarity framework and previous theoretical developments on the subject, the present QQSPR procedure relies on the possibility to perform geometrical origin shifts over molecular density function sets. In this way, molecular collections attached to known properties can be easily used over other quantum mechanically well-described molecular structures for the estimation of their unknown property values. The proposed procedure takes quantum mechanical expectation value as provider of causal relation background and overcomes the dimensionality paradox, which haunts classical descriptor space QSPR. Also, contrarily to classical procedures, which are also attached to heavy statistical gear, the present QQSPR approach might use a geometrical assessment only or just some simple statistical outline or both. From an applied point of view, several easily reachable computational levels can be set up. A Fortran 95 program: QQSPR-n is described with two versions, which might be downloaded from a dedicated web site. Various practical examples are provided, yielding excellent results. Finally, it is also shown that an equivalent molecular space classical QSPR formalism can be easily developed. PMID:23238931

  17. Quantitative structure-property relationships on photolysis of PCDD/Fs adsorbed to spruce (Picea abies (L.) Karst.) needle surfaces under sunlight irradiation.

    PubMed

    Niu, Junfeng; Huang, Liping; Chen, Jingwen; Yu, Gang; Schramm, Karl-Werner

    2005-02-01

    By partial least squares (PLS) regression, quantitative structure-property relationship (QSPR) models were developed for photolysis half-life (t1/2) of PCDD/Fs and PAHs sorbed to spruce (Picea abies (L.) Karst.) needle surfaces and irradiated by sunlight. Quantum chemical descriptors computed by PM3 Hamiltonian were used predictor variables. PLS analysis for the PCDDs and PAHs respectively resulted in no correlation by our statistical methods. The cross-validated Qcum2 value for the optimal QSPR model of PCDFs is 0.722, indicating a good predictive ability for logt1/2 of PCDFs adsorbed to spruce needle surfaces. The QSPR results show that the number of chlorine atoms bonded to the parent structure and (E(LUMO)-E(HOMO))2 has a dominant effect on t1/2 values of PCDFs. Increasing the number of chlorine atoms and (E(LUMO)-E(HOMO))2 values leads to increase of logt1/2 values of PCDFs. PMID:15639263

  18. Quantitative Structure-Property Relationship (QSPR) Models for a Local Quantum Descriptor: Investigation of the 4- and 3-Substituted-Cinnamic Acid Esterification.

    PubMed

    Rodrigues-Santos, Cláudio E; Echevarria, Aurea; Sant'Anna, Carlos M R; Bitencourt, Thiago B; Nascimento, Maria G; Bauerfeldt, Glauco F

    2015-01-01

    In this work, the theoretical description of the 4- and 3-substituted-cinnamic acid esterification with different electron donating and electron withdrawing groups was performed at the B3LYP and M06-2X levels, as a two-step process: the O-protonation and the nucleophile attack by ethanol. In parallel, an experimental work devoted to the synthesis and characterization of the substituted-cinnamate esters has also been performed. In order to quantify the substituents effects, quantitative structure-property relationship (QSPR) models based on the atomic charges, Fukui functions and the Frontier Effective-for-Reaction Molecular Orbitals (FERMO) energies were investigated. In fact, the Fukui functions, ƒ⁺C and ƒ(-)O, indicated poor correlations for each individual step, and in contrast with the general literature, the O-protonation step is affected both by the FERMO energies and the O-charges of the carbonyl group. Since the process was shown to not be totally described by either charge- or frontier-orbitals, it is proposed to be frontier-charge-miscere controlled. Moreover, the observed trend for the experimental reaction yields suggests that the electron withdrawing groups favor the reaction and the same was observed for Step 2, which can thus be pointed out as the determining step. PMID:26402661

  19. Linear and nonlinear quantitative structure-property relationship models for solubility of some anthraquinone, anthrone and xanthone derivatives in supercritical carbon dioxide.

    PubMed

    Hemmateenejad, Bahram; Shamsipur, Mojtaba; Miri, Ramin; Elyasi, Maryam; Foroghinia, Farzaneh; Sharghi, Hashem

    2008-03-01

    A quantitative structure-property relation (QSPR) study was conducted on the solubility in supercritical fluid carbon dioxide (SCF-CO2) of some recently synthesized anthraquinone, anthrone and xanthone derivatives. The data set consisted of 29 molecules in various temperatures and pressures, which form 1190 solubility data. The combined data splitting-feature selection (CDFS) strategy, which previously developed in our research group, was used as descriptor selection and model development method. Modeling of the relationship between selected molecular descriptors and solubility data was achieved by linear (multiple linear regression; MLR) and nonlinear (artificial neural network; ANN) methods. The QSPR models were validated by cross-validation as well as application of the models to predict the solubility of three external set compounds, which did not have contribution in model development steps. Both linear and nonlinear methods resulted in accurate prediction whereas more accurate results were obtained by ANN model. The respective root mean square error of prediction obtained by MLR and ANN models were 0.284 and 0.095 in the term of logarithm of g solute m(-3) of SCF-CO2. A comparison was made between the models selected by CDFS method and the conventional stepwise feature selection method. It was found that the latter produced models with higher number of descriptors and lowered prediction ability, thus it can be considered as an over-fitted model. PMID:18267136

  20. Quantitative structure-property relationship (QSPR) for the adsorption of organic compounds onto activated carbon cloth: Comparison between multiple linear regression and neural network

    SciTech Connect

    Brasquet, C.; Bourges, B.; Le Cloirec, P.

    1999-12-01

    The adsorption of 55 organic compounds is carried out onto a recently discovered adsorbent, activated carbon cloth. Isotherms are modeled using the Freundlich classical model, and the large database generated allows qualitative assumptions about the adsorption mechanism. However, to confirm these assumptions, a quantitative structure-property relationship methodology is used to assess the correlations between an adsorbability parameter (expressed using the Freundlich parameter K) and topological indices related to the compounds molecular structure (molecular connectivity indices, MCI). This correlation is set up by mean of two different statistical tools, multiple linear regression (MLR) and neural network (NN). A principal component analysis is carried out to generate new and uncorrelated variables. It enables the relations between the MCI to be analyzed, but the multiple linear regression assessed using the principal components (PCs) has a poor statistical quality and introduces high order PCs, too inaccurate for an explanation of the adsorption mechanism. The correlations are thus set up using the original variables (MCI), and both statistical tools, multiple linear regression and neutral network, are compared from a descriptive and predictive point of view. To compare the predictive ability of both methods, a test database of 10 organic compounds is used.

  1. On the Development and Use of Large Chemical Similarity Networks, Informatics Best Practices and Novel Chemical Descriptors Towards Materials Quantitative Structure Property Relationships

    NASA Astrophysics Data System (ADS)

    Krein, Michael

    After decades of development and use in a variety of application areas, Quantitative Structure Property Relationships (QSPRs) and related descriptor-based statistical learning methods have achieved a level of infamy due to their misuse. The field is rife with past examples of overtrained models, overoptimistic performance assessment, and outright cheating in the form of explicitly removing data to fit models. These actions do not serve the community well, nor are they beneficial to future predictions based on established models. In practice, in order to select combinations of descriptors and machine learning methods that might work best, one must consider the nature and size of the training and test datasets, be aware of existing hypotheses about the data, and resist the temptation to bias structure representation and modeling to explicitly fit the hypotheses. The definition and application of these best practices is important for obtaining actionable modeling outcomes, and for setting user expectations of modeling accuracy when predicting the endpoint values of unknowns. A wide variety of statistical learning approaches, descriptor types, and model validation strategies are explored herein, with the goals of helping end users understand the factors involved in creating and using QSPR models effectively, and to better understand relationships within the data, especially by looking at the problem space from multiple perspectives. Molecular relationships are commonly envisioned in a continuous high-dimensional space of numerical descriptors, referred to as chemistry space. Descriptor and similarity metric choice influence the partitioning of this space into regions corresponding to local structural similarity. These regions, known as domains of applicability, are most likely to be successfully modeled by a QSPR. In Chapter 2, the network topology and scaling relationships of several chemistry spaces are thoroughly investigated. Chemistry spaces studied include the

  2. Explorations of molecular structure-property relationships.

    PubMed

    Seybold, P G

    1999-01-01

    The problem of the relationship between the structure of a molecule and its physical, chemical, and biological properties is one of the most fundamental in chemistry. Three molecular structure-property studies are discussed as illustrations of different approaches to this problem. In the first study the carcinogenic activities of polycyclic aromatic hydrocarbons and their derivatives are examined. Molecular orbital calculations of the presumptive activation steps and species for these compounds (based on the "bay region" theory of activation) are seen to yield a surprisingly good guide to the observed carcinogenic activities. Both activation and deactivation steps are considered. The second study reviews structure-property work on the tissue solubilities of halogenated hydrocarbons. Relatively simple structural descriptors give a good account of the solubilities of these compounds in blood, muscle, fat, and liver tissue. With the aid of principal components analysis it is shown that there are two dominant dimensions to this problem, which can be interpreted in terms of solubilities of the compounds in lipid and saline environments. The final study, which examines the boiling points of aliphatic alcohols, illustrates the value of using more than one descriptor set. The (perhaps surprising) conclusion is that a theoretical model can sometimes be more accurate than the data upon which it is based. Moreover, two models are better than one. PMID:10491848

  3. Structure-property Relationships of Layered Oxypnictides

    NASA Astrophysics Data System (ADS)

    Muir, Sean W.

    Investigating the structure-property relationships of solid state materials can help improve many of the materials we use each day in life. It can also lead to the discovery of materials with interesting and unforeseen properties. In this work the structure property relationships of newly discovered layered oxypnictide phases are presented and discussed. There has generally been worldwide interest in layered oxypnictide materials following the discovery of superconductivity up to 55 K for iron arsenides such as LnFeAsO 1-xFx (where Ln = Lanthanoid). This work presents efforts to understand the structure and physical property changes which occur to LnFeAsO materials when Fe is replaced with Rh or Ir and when As is replaced with Sb. As part of this work the solid solution between LaFeAsO and LaRhAsO was examined and superconductivity is observed for low Rh content with a maximum critical temperature of 16 K. Ln RhAsO and LnIrAsO compositions are found to be metallic; however Ce based compositions display a resistivity temperature dependence which is typical of Kondo lattice materials. At low temperatures a sudden drop in resistivity occurs for both CeRhAsO and CeIrAsO compositions and this drop coincides with an antiferromagnetic transition. The Kondo scattering temperatures and magnetic transition temperatures observed for these materials can be rationalized by considering the expected difference in N(EF) J parameters between them, where N(EF) is the density of states at the Fermi level and J represents the exchange interaction between the Ce 4f1 electrons and the conduction electrons. In addition to studying these 4d and 5d substituted systems the LaFeSbO compositional system was investigated. While LaFeSbO has not been successfully synthesized the transition metal free layered oxypnictide composition La2SbO 2 was discovered and its structural and physical properties have been examined along with the properties of La2BiO2. Density functional theory was used to

  4. A Quantitative Structure-Property Relationship (QSPR) Study of Aliphatic Alcohols by the Method of Dividing the Molecular Structure into Substructure

    PubMed Central

    Liu, Fengping; Cao, Chenzhong; Cheng, Bin

    2011-01-01

    A quantitative structure–property relationship (QSPR) analysis of aliphatic alcohols is presented. Four physicochemical properties were studied: boiling point (BP), n-octanol–water partition coefficient (lg POW), water solubility (lg W) and the chromatographic retention indices (RI) on different polar stationary phases. In order to investigate the quantitative structure–property relationship of aliphatic alcohols, the molecular structure ROH is divided into two parts, R and OH to generate structural parameter. It was proposed that the property is affected by three main factors for aliphatic alcohols, alkyl group R, substituted group OH, and interaction between R and OH. On the basis of the polarizability effect index (PEI), previously developed by Cao, the novel molecular polarizability effect index (MPEI) combined with odd-even index (OEI), the sum eigenvalues of bond-connecting matrix (SX1CH) previously developed in our team, were used to predict the property of aliphatic alcohols. The sets of molecular descriptors were derived directly from the structure of the compounds based on graph theory. QSPR models were generated using only calculated descriptors and multiple linear regression techniques. These QSPR models showed high values of multiple correlation coefficient (R > 0.99) and Fisher-ratio statistics. The leave-one-out cross-validation demonstrated the final models to be statistically significant and reliable. PMID:21731451

  5. Structure Property Relationships of Carboxylic Acid Isosteres

    PubMed Central

    2016-01-01

    The replacement of a carboxylic acid with a surrogate structure, or (bio)-isostere, is a classical strategy in medicinal chemistry. The general underlying principle is that by maintaining the features of the carboxylic acid critical for biological activity, but appropriately modifying the physicochemical properties, improved analogs may result. In this context, a systematic assessment of the physicochemical properties of carboxylic acid isosteres would be desirable to enable more informed decisions of potential replacements to be used for analog design. Herein we report the structure–property relationships (SPR) of 35 phenylpropionic acid derivatives, in which the carboxylic acid moiety is replaced with a series of known isosteres. The data set generated provides an assessment of the relative impact on the physicochemical properties that these replacements may have compared to the carboxylic acid analog. As such, this study presents a framework for how to rationally apply isosteric replacements of the carboxylic acid functional group. PMID:26967507

  6. Structure-property relationships of bismaleimides

    NASA Astrophysics Data System (ADS)

    Tenteris-Noebe, Anita Diane

    The purpose of this research was to control and systematically vary the network topology of bismaleimides through cure temperature and chemistry (addition of various coreactants) and subsequently attempt to determine structure-mechanical property relationships. Characterization of the bismaleimide structures by dielectric, rheological, and thermal analyses, and density measurements was subsequently correlated with mechanical properties such as modulus, yield strength, fracture energy, and stress relaxation. The model material used in this investigation was 4,4sp'-bismaleimidodiphenyl methane (BMI). BMI was coreacted with either 4,4sp'-methylene dianiline (MDA), o,osp'-diallyl bisphenol A (DABA) from Ciba Geigy, or diamino diphenyl sulfone (DDS). Three cure paths were employed: a low-temperature cure of 140sp°C where chain extension should predominate, a high-temperature cure of 220sp°C where both chain extension and crosslinking should occur simultaneously, and a low-temperature (140sp°C) cure followed immediately by a high-temperature (220sp°C) cure where the chain extension reaction or amine addition precedes BMI homopolymerization or crosslinking. Samples of cured and postcured PMR-15 were also tested to determine the effects of postcuring on the mechanical properties. The low-temperature cure condition of BMI/MDA exhibited the highest modulus values for a given mole fraction of BMI with the modulus decreasing with decreasing concentration of BMI. The higher elastic modulus is the result of steric hindrance by unreacted BMI molecules in the glassy state. The moduli values for the high- and low/high-temperature cure conditions of BMI/MDA decreased as the amount of diamine increased. All the moduli values mimic the yield strength and density trends. For the high-temperature cure condition, the room-temperature modulus remained constant with decreasing mole fraction of BMI for the BMI/DABA and BMI/DDS systems. Postcuring PMR-15 increases the modulus over that

  7. Structure-Property Relationships of Bismaleimides

    NASA Technical Reports Server (NTRS)

    Tenteris-Noebe, Anita D.

    1997-01-01

    The purpose of this research was to control and systematically vary the network topology of bismaleimides through cure temperature and chemistry (addition of various coreactants) and subsequently attempt to determine structure-mechanical property relationships. Characterization of the bismaleimide structures by dielectric, rheological, and thermal analyses, and density measurements was subsequently correlated with mechanical properties such as modulus, yield strength, fracture energy, and stress relaxation. The model material used in this investigation was 4,4'-BismaleiMidodIphenyl methane (BMI). BMI was coreacted with either 4,4'-Methylene Dianiline (MDA), o,o'-diallyl bisphenol A (DABA) from Ciba Geigy, or Diamino Diphenyl Sulfone (DDS). Three cure paths were employed: a low- temperature cure of 140 C where chain extension should predominate, a high-temperature cure of 220 C where both chain extension and crosslinking should occur simultaneously, and a low-temperature (140 C) cure followed immediately by a high-temperature (220 C) cure where the chain extension reaction or amine addition precedes BMI homopolymerization or crosslinking. Samples of cured and postcured PMR-15 were also tested to determine the effects of postcuring on the mechanical properties. The low-temperature cure condition of BMI/MDA exhibited the highest modulus values for a given mole fraction of BMI with the modulus decreasing with decreasing concentration of BMI. The higher elastic modulus is the result of steric hindrance by unreacted BMI molecules in the glassy state. The moduli values for the high- and low/high-temperature cure conditions of BMI/MDA decreased as the amount of diamine increased. All the moduli values mimic the yield strength and density trends. For the high-temperature cure condition, the room- temperature modulus remained constant with decreasing mole fraction of BMT for the BMI/DABA and BMI/DDS systems. Postcuring PMR-15 increases the modulus over that of the cured

  8. Structure-property Relationships for Methyl-terminated Alkyl Self-assembled Monolayers

    SciTech Connect

    F DelRio; D Rampulla; C Jaye; G Stan; R Gates; D Fischer; R Cook

    2011-12-31

    Structure-property relationships for methyl-terminated alkyl self-assembled monolayers (SAMs) are developed using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and atomic force microscopy (AFM). NEXAFS C K-edge spectra are used to compute the dichroic ratio, which provides a quantitative measure of the molecular structure. AFM data are analyzed with an elastic adhesive contact model, modified by a first-order elastic perturbation method to include substrate effects, to extract the monolayer mechanical properties. Using this approach, the measured mechanical properties are not influenced by the substrate, which allows universal structure-property relationships to be developed for methyl-terminated alkyl SAMs.

  9. Structure-property relationships of nanoscale engineered perovskite oxides

    NASA Astrophysics Data System (ADS)

    Tian, Wei

    Recent advances in the synthesis of nanoscale customized structure have demonstrated that reactive molecular beam epitaxy (MBE) can be used to construct nanostructure of oxides with atomic control. The ability to engineer the structure and chemistry of oxides at the nanometer scale makes possible for the creation of new functional materials that can be designed to have exceptional properties. This thesis focused on understanding structure-property relationships of such nanoscale customized oxides utilizing state-of-the-art transmission electron microscopy (TEM). Epitaxial thin films of n = 1--5 members of Ruddlesden-Popper homologous series Srn+1Ti nO3n+1 were synthesized by reactive MBE. We investigated the structure and microstructure of these thin films by x-ray diffraction along with high-resolution transmission electron microscopy (HRTEM) in combination with computer image simulations. We found that the thin films of n = 1--3 members are nearly free of intergrowths, e.g. phase-pure, while n = 4 and 5 thin films contain noticeably more intergrowth defects and anti-phase boundaries in their perovskite sheets. We show that these results are consistent with what is known about the thermodynamics of Sr n+1TinO3 n+1 phases. We also investigated the atomic structure and interfacial structure of artificial PbTiO3/SrTiO3 and BaTiO3/SrTiO 3 superlattices grown by MBE both with and without digital compositional grading. Both of these systems form a solid solution over their entire composition range. Thus, these layered heterostructures are metastable. We demonstrated, however, that the thermodynamically metastable superlattices can be kinetically stabilized via layer-by-layer growth. In addition, we found that the interfaces between two constituents in the heterostructures are atomically-abrupt. The superlattice thin films were made fully coherent with the substrates, resulting in a homogeneous large strain in the BaTiO3 layers due to the lattice mismatch between BaTiO3

  10. Structure-Property Relationships of Solids in Pharmaceutical Processing

    NASA Astrophysics Data System (ADS)

    Chattoraj, Sayantan

    Pharmaceutical development and manufacturing of solid dosage forms is witnessing a seismic shift in the recent years. In contrast to the earlier days when drug development was empirical, now there is a significant emphasis on a more scientific and structured development process, primarily driven by the Quality-by-Design (QbD) initiatives of US Food and Drug Administration (US-FDA). Central to such an approach is the enhanced understanding of solid materials using the concept of Materials Science Tetrahedron (MST) that probes the interplay between four elements, viz., the structure, properties, processing, and performance of materials. In this thesis work, we have investigated the relationships between the structure and those properties of pharmaceutical solids that influence their processing behavior. In all cases, we have used material-sparing approaches to facilitate property assessment using very small sample size of materials, which is a pre-requisite in the early stages of drug development when the availability of materials, drugs in particular, is limited. The influence of solid structure, either at the molecular or bulk powder levels, on crystal plasticity and powder compaction, powder flow, and solid-state amorphization during milling, has been investigated in this study. Through such a systematic evaluation, we have captured the involvement of structure-property correlations within a wide spectrum of relevant processing behaviors of pharmaceutical solids. Such a holistic analysis will be beneficial for addressing both regulatory and scientific issues in drug development.

  11. Structure property relationships of carbonaceous films grown under ion enhancement

    SciTech Connect

    Weissmantel, C.; Ackermann, E.; Bewilogua, K.; Hecht, G.; Kupfer, H.; Rau, B.

    1986-11-01

    Based on our own results and in comparison with data published by other groups the structure property relationships of carbon and carbon/metal films prepared by sputtering and deposition of partially ionized species are discussed. Films grown by ion beam sputtering are dark brownish and amorphous with a small fraction of microcrystals. However, a transition to transparent and insulating layers can be effected by ion bombardment. C/Me coatings, where Me stands for Ti or Sn, were obtained by magnetron sputtering of composite targets. The films proved to be amorphous up to metal concentrations of more than 10 at. %, but metal and carbide crystals grow upon annealing. Measurements of the hardness, the electrical conductivity, and the contact behavior in dependence on the composition provided interesting information. For carbon films prepared by deposition of partially ionized benzene species it has been found that the properties depend characteristically on the ion energy; typical ''diamondlike'' i-C films are obtained by applying a bias voltage from 1--3 keV. The thermal stability of the amorphous coatings is discussed in conjunction with their electrical conductivity. Summarizing extensive structure investigations, a structure model based on tetrahedrally interlinked carbon rings is proposed. Composites of the type i-C/Me (Me: Al, Ti, Cr), which were prepared by simultaneous metal evaporation, exhibit a wide range of structure property relations.

  12. Structure-Property Relationship in High Tg Thermosetting Polyimides

    NASA Technical Reports Server (NTRS)

    Chuang, Kathy C.; Meador, Mary Ann B.; HardyGreen, DeNise

    2000-01-01

    This viewgraph presentation gives an overview of the structure-property relationship in high glass transition temperatures (T(sub g)) thermosetting polyimides. The objectives of this work are to replace MDA in PMR-15 with 2,2-substituted benzidine and to evaluate the thermo-oxidative stability and mechanical properties of DMBZ-15 against PMR-15. Details are given on the T(sub g) of polyimide resins, the x-ray crystal structure of 2,2-Bis(trifluoro)benzidine (BFBZ), the isothermal aging of polyimide resins at 288 C under 1 atm of circulating air, the compressive strength of polyimide composites, and a gas evaluation profile of DMBZ-15 polyimide resins.

  13. Oxide Thermoelectric Materials: A Structure-Property Relationship

    NASA Astrophysics Data System (ADS)

    Nag, Abanti; Shubha, V.

    2014-04-01

    Recent demand for thermoelectric materials for power harvesting from automobile and industrial waste heat requires oxide materials because of their potential advantages over intermetallic alloys in terms of chemical and thermal stability at high temperatures. Achievement of thermoelectric figure of merit equivalent to unity ( ZT ≈ 1) for transition-metal oxides necessitates a second look at the fundamental theory on the basis of the structure-property relationship giving rise to electron correlation accompanied by spin fluctuation. Promising transition-metal oxides based on wide-bandgap semiconductors, perovskite and layered oxides have been studied as potential candidate n- and p-type materials. This paper reviews the correlation between the crystal structure and thermoelectric properties of transition-metal oxides. The crystal-site-dependent electronic configuration and spin degeneracy to control the thermopower and electron-phonon interaction leading to polaron hopping to control electrical conductivity is discussed. Crystal structure tailoring leading to phonon scattering at interfaces and nanograin domains to achieve low thermal conductivity is also highlighted.

  14. Computational design and structure-property relationship studies on heptazines.

    PubMed

    Ghule, Vikas D; Sarangapani, Radhakrishnan; Jadhav, Pandurang M; Pandey, Raj Kishore

    2011-11-01

    This study aimed to design novel nitrogen-rich heptazine derivatives as high energy density materials (HEDM) by exploiting systematic structure-property relationships. Molecular structures with diverse energetic substituents at varying positions in the basic heptazine ring were designed. Density functional techniques were used for prediction of gas phase heat of formation by employing an isodesmic approach, while crystal density was assessed by packing calculations. The results reveal that nitro derivatives of heptazine possess a high heat of formation and further enhancement was achieved by the substitution of nitro heterocycles. The crystal packing density of the designed compounds varied from 1.8 to 2 g cm(-3), and hence, of all the designed molecules, nitro derivatives of heptazine exhibit better energetic performance characteristics in terms of detonation velocity and pressure. The calculated band gap of the designed molecules was analyzed to establish sensitivity correlations, and the results reveal that, in general, amino derivatives possess better insensitivity characteristics. The overall performance of the designed compounds was moderate, and such compounds may find potential applications in gas generators and smoke-free pyrotechnic fuels as they are rich in nitrogen content. PMID:21318236

  15. Processing-structure-property relationships in oriented polymers

    NASA Astrophysics Data System (ADS)

    Xia, Zhiyong

    The Processing-Structure-Property (P-S-P) relationships in oriented polymers have been studied in this dissertation. Controlled polymer orientation has been achieved through the equal channel angular extrusion (ECAE) process. The structure of the ECAE-oriented polymers have been investigated from all dimensional levels, i.e., from spherulitical scale (micrometer scale), lamellar scale (nanometer scale) to crystallographic scale (angstrom scale). The results indicate that the polymer spherulites are deformed into macrofibrils after one ECAE process. Within the macrofibrils, a "V-type" lamellar orientation has been formed to accommodate the overall straining of spherulites. The molecular chains in the crystalline lamellae are found to be tilted at a small angle with respect to the lamellar surface. Whereas, the molecular chains between the macrofibrils and crystalline lamellae are highly stretched. Property characterization indicates that ECAE-induced microstructure is responsible for the improved physical and mechanical properties. The improved physical and mechanical properties include high tensile modulus, higher impact fracture toughness and better scratch resistance. This research has also clarified several controversies in the research of semicrystalline polymers. First, this research gives an unambiguous account on the lamellar evolution during large-scale plastic deformation. The crystalline lamellae in the ECAE-oriented samples have been found to be evolved from the original crystalline lamellae. Secondly, the shifting of the primary relaxation peak in ECAE-oriented PET has been found to be due to the increase in molecular orientation. Thirdly, the transmission electron microscopy (TEM) indicates that in low crystallinity semicrystalline polymers, the larger value of the two characteristic lengths from small angle X-ray scattering (SAXS) correlation function analysis should be assigned to the crystalline lamellar thickness.

  16. Structure-property relationships in polymers for dielectric capacitors

    NASA Astrophysics Data System (ADS)

    Gupta, Sahil

    Effective energy storage is a key challenge of the 21st century that has fueled research in the area of energy storage devices. In this dissertation, structure-property relationships have been evaluated for polymers that might be suitable for storing energy in high-energy density, high-temperature capacitors. Firstly, hydroxyl-modified polypropylenes (PPOH) were synthesized by copolymerization of the propylene and undecenyloxytrimethylsilane monomers. The presence of H-bonding in PPOH copolymers increased their glass-transition temperature. Steric hindrance by the comonomer reduced the PP crystal growth rate and crystal size, resulting in a melting point depression. The comonomer was restricted outside the crystalline domains leaving the alpha-monoclinic crystal structure of PP unaffected, but increasing the fold-surface free energy. Crystallization was slower for PPOH copolymers than PP, but exhibited a skewed bell curve as a function of hydroxyl concentration. H-bonding persisted even at melt temperatures up to 250°C resulting in a higher elasticity and viscosity for PPOH copolymers. Secondly, sulfonated poly(ether ether ketone) (HSPEEK) was synthesized by sulfonating PEEK with sulfuric acid, and further neutralized with Zn to obtain ZnSPEEK. The thermal and dielectric properties of SPEEK were compared with PEEK. The glass-transition increased and melting point were high enough to enable the use of polymer at 180°C. The incorporation of sulfonic groups in PEEK increased the dielectric constant. HSPEEK had a higher dielectric constant than ZnSPEEK due to higher dipolar mobility, but the dielectric loss was also higher for HSPEEK due to electrode polarization and DC conduction. These results were consistent with our observations from sulfonated polystyrene (HSPS), which was used as a >model&lang' polymer. Lastly, commercial poly(4-methyl-1-pentene) (P4MP) was characterized to check its viability as a high-temperature polymer dielectric. Thermal stability up to

  17. Structure-property relationships in graphene/polymer nanocomposites

    NASA Astrophysics Data System (ADS)

    Iqbal, Muhammad Z.

    Graphene's unique combination of excellent electrical, thermal, and mechanical properties can provide multi-functional reinforcement for polymer nanocomposites. However, poor dispersion of graphene in non-polar polyolefins limits its applications as a universal filler. Thus, the overall goal of this thesis was to improve graphene's dispersion in graphene/polyolefin nanocomposites and develop processing-structure-property relationships. A new polymer matrix was synthesized by blending polyethylene (PE) with oxidized polyethylene (OPE). Inclusion of OPE in PE produced miscible blends, but the miscibility decreased with increasing OPE loading. Meanwhile, the Young's modulus of blends increased with increasing OPE concentration, attributed to decreased long period order in PE and increased crystallinity. In addition, the miscibility of OPE in PE substantially reduced the viscosity of blends. Using thermally reduced graphene (TRG) produced by simultaneous thermal exfoliation and reduction of graphite oxide, electrically conductive nanocomposites were manufactured by incorporating TRG in PE/OPE blends via solution blending. The rheological and electrical percolations decreased substantially to 0.3 and 0.13 vol% of TRG in PE/OPE/TRG nanocomposites compared to 1.0 and 0.3 vol% in PE/TRG nanocomposites. Improved dispersion of TRG in blends was attributed to increased TRG/polymer interactions, leading to high aspect ratio of the dispersed TRG. A universal Brownian dispersion mechanism for graphene was concluded similar to that of carbon nanotubes, following the Doi-Edwards theory. Furthermore, the improved dispersion of TRG correlated with the formation of surface fractals in PE/OPE/TRG nanocomposites, whereas the poor dispersion of TRG in PE led to the formation of only mass fractals. Moreover, graphene and carbon black (CB) were combined as a synergic filler for manufacturing electrically conductive PE nanocomposites. Smaller fractals were observed at lower CB

  18. Structure-property relationships of multiferroic materials: A nano perspective

    NASA Astrophysics Data System (ADS)

    Bai, Feiming

    The integration of sensors, actuators, and control systems is an ongoing process in a wide range of applications covering automotive, medical, military, and consumer electronic markets. Four major families of ceramic and metallic actuators are under development: piezoelectrics, electrostrictors, magnetostrictors, and shape-memory alloys. All of these materials undergo at least two phase transformations with coupled thermodynamic order parameters. These transformations lead to complex domain wall behaviors, which are driven by electric fields (ferroelectrics), magnetic fields (ferromagnetics), or mechanical stress (ferroelastics) as they transform from nonferroic to ferroic states, contributing to the sensing and actuating capabilities. This research focuses on two multiferroic crystals, Pb(Mg1/3Nb 2/3)O3-PbTiO3 and Fe-Ga, which are characterized by the co-existence and coupling of ferroelectric polarization and ferroelastic strain, or ferro-magnetization and ferroelastic strain. These materials break the conventional boundary between piezoelectric and electrostrictors, or magnetostrictors and shape-memory alloys. Upon applying field or in a poled condition, they yield not only a large strain but also a large strain over field ratio, which is desired and much benefits for advanced actuator and sensor applications. In this thesis, particular attention has been given to understand the structure-property relationships of these two types of materials from atomic to the nano/macro scale. X-ray and neutron diffraction were used to obtain the lattice structure and phase transformation characteristics. Piezoresponse and magnetic force microscopy were performed to establish the dependence of domain configurations on composition, thermal history and applied fields. It has been found that polar nano regions (PNRs) make significant contributions to the enhanced electromechanical properties of PMN-x%PT crystals via assisting intermediate phase transformation. With increasing PT

  19. Structure-property relationships in silica-siloxane nanocomposite materials

    SciTech Connect

    Ulibarri, T.A.; Derzon, D.K.; Wang, L.C.

    1997-03-01

    The simultaneous formation of a filler phase and a polymer matrix via in situ sol-gel techniques provides silica-siloxane nanocomposite materials of high strength. This study concentrates on the effects of temperature and relative humidity on a trimodal polymer system in an attempt to accelerate the reaction as well as evaluate subtle process- structure-property relations. It was found that successful process acceleration is only viable for high humidity systems when using the tin(IV) catalyst dibutyltin dilaurate. Processes involving low humidity were found to be very temperature and time dependent. Bimodal systems were investigated and demonstrated that the presence of a short-chain component led to enhanced material strength. This part of the study also revealed a link between the particle size and population density and the optimization of material properties.

  20. Structure-property relationships of flexible polyurethane foams

    NASA Astrophysics Data System (ADS)

    Aneja, Ashish

    This study examined several features of flexible polyurethane foams from a structure-property perspective. A major part of this dissertation addresses the issue of connectivity of the urea phase and its influence on mechanical and viscoelastic properties of flexible polyurethane foams and their plaque counterparts. Lithium salts (LiCl and LiBr) were used as additives to systematically alter the phase separation behavior, and hence the connectivity of the urea phase at different scale lengths. Macro connectivity, or the association of the large scale urea rich aggregates typically observed in flexible polyurethane foams was assessed using SAXS, TEM, and AFM. These techniques showed that including a lithium salt in the foam formulation suppressed the formation of the urea aggregates and thus led to a loss in the macro level connectivity of the urea phase. WAXS and FTIR were used to demonstrate that addition of LiCl or LiBr systematically disrupted the local ordering of the hard segments within the microdomains, i.e., it led to a reduction of micro level connectivity or the regularity in segmental packing of the urea phase. Based on these observations, the interaction of the lithium salt was thought to predominantly occur with the urea hard segments, and this hypothesis was confirmed using quantum mechanical calculations. Another feature of this research investigated model trisegmented polyurethanes based on monofunctional polyols, or "monos", with water-extended toluene diisocyanate (TDI) based hard segments. The formulations of the monol materials were maintained similar to those of flexible polyurethane foams with the exceptions that the conventional polyol was substituted by an oligomeric monofunctional polyether of ca. 1000 g/mol molecular weight. Plaques formed from these model systems were shown to be solid materials even at their relatively low molecular weights of 3000 g/mol and less, AFM phase images, for the first time, revealed the ability of the hard

  1. Incoloy 908 database report: On process -- structure -- property relationship

    SciTech Connect

    Toma, L.S.; Hwang, I.S.; Steeves, M.M.

    1993-05-01

    Incoloy 908 is a nickel-iron base superalloy with a coefficient of expansion (COE) and mechanical properties that have been optimized for use in Nb{sub 3}Sn superconducting magnets. It has been proposed for use as a conduit material for the International Thermonuclear Experimental Reactor (ITER) magnets. The relationship between manufacturing processes, microstructures and mechanical properties of Incoloy 908 are characterized in support of the magnet fabrication and quality control. This report presents microhardness, microstructure, and yield and ultimate tensile strengths as functions of thermomechanical process variables including heat treatment, annealing and cold work for laboratory prepared Incoloy 908 specimens. Empirical correlations have been developed for the microhardness at room temperature and tensile strength at room temperature and at 4K. These results may be used for manufacturing quality control or for design.

  2. An Investigation of College Chemistry Students' Understanding of Structure-Property Relationships

    ERIC Educational Resources Information Center

    Cooper, Melanie M.; Corley, Leah M.; Underwood, Sonia M.

    2013-01-01

    The connection between the molecular-level structure of a substance and its macroscopic properties is a fundamental concept in chemistry. Students in college-level general and organic chemistry courses were interviewed to investigate how they used structure-property relationships to predict properties such as melting and boiling points. Although…

  3. Processing-structure-property relationships of carbon nanotube and nanoplatelet enabled piezoresistive sensors

    NASA Astrophysics Data System (ADS)

    Luo, Sida

    Individual carbon nanotubes (CNTs) possess excellent piezoresistive performance, which is manifested by the significant electrical resistance change when subject to mechanical deformation. In comparison to individual CNTs, the CNT thin films, formed by a random assembly of individual tubes or bundles, show much lower piezoresistive sensitivity. Given the progress made to date in developing CNT ensemble based-piezoresistive sensors, the related piezoresistive mechanism(s) are still not well understood. The crucial step to obtain a better understanding of this issue is to study the effects of CNT structure in the dispersion on the piezoresistivity of CNT ensemble based-piezoresistive sensors. To reach this goal, my Ph.D. research first focuses on establishing the processing-structure-property relationship of SWCNT thin film piezoresistive sensors. The key accomplishment contains: 1) developing the combined preparative ultracentrifuge method (PUM) and dynamic light scattering (DLS) method to quantitatively characterized SWCNT particle size in dispersions under various sonication conditions; 2) designing combined ultrasonication and microfluidization processing protocol for high throughput and large-scale production of high quality SWCNT dispersions; 3) fabricating varied SWCNT thin film piezoresistive sensors through spray coating technique and immersion-drying post-treatment; and 4) investigating the effect of microstructures of SWCNTs on piezoresistivity of SWCNT thin film sensors. This experimental methodology for quantitative and systematic investigation of the processing-structure-property relationships provides a means for the performance optimization of CNT ensemble based piezoresistive sensors. As a start to understand the piezoresistive mechanism, the second focus of my Ph.D. research is studying charge transport behaviors in SWCNT thin films. It was found that the temperature-dependent sheet resistance of SWCNT thin films could be explained by a 3D variable

  4. Grain Boundary Plane Orientation Fundamental Zones and Structure-Property Relationships

    PubMed Central

    Homer, Eric R.; Patala, Srikanth; Priedeman, Jonathan L.

    2015-01-01

    Grain boundary plane orientation is a profoundly important determinant of character in polycrystalline materials that is not well understood. This work demonstrates how boundary plane orientation fundamental zones, which capture the natural crystallographic symmetries of a grain boundary, can be used to establish structure-property relationships. Using the fundamental zone representation, trends in computed energy, excess volume at the grain boundary, and temperature-dependent mobility naturally emerge and show a strong dependence on the boundary plane orientation. Analysis of common misorientation axes even suggests broader trends of grain boundary energy as a function of misorientation angle and plane orientation. Due to the strong structure-property relationships that naturally emerge from this work, boundary plane fundamental zones are expected to simplify analysis of both computational and experimental data. This standardized representation has the potential to significantly accelerate research in the topologically complex and vast five-dimensional phase space of grain boundaries. PMID:26498715

  5. Grain boundary plane orientation fundamental zones and structure-property relationships

    DOE PAGESBeta

    Homer, Eric R.; Patala, Srikanth; Priedeman, Jonathan L.

    2015-10-26

    Grain boundary plane orientation is a profoundly important determinant of character in polycrystalline materials that is not well understood. This work demonstrates how boundary plane orientation fundamental zones, which capture the natural crystallographic symmetries of a grain boundary, can be used to establish structure-property relationships. Using the fundamental zone representation, trends in computed energy, excess volume at the grain boundary, and temperature-dependent mobility naturally emerge and show a strong dependence on the boundary plane orientation. Analysis of common misorientation axes even suggests broader trends of grain boundary energy as a function of misorientation angle and plane orientation. Due to themore » strong structure-property relationships that naturally emerge from this work, boundary plane fundamental zones are expected to simplify analysis of both computational and experimental data. This standardized representation has the potential to significantly accelerate research in the topologically complex and vast five-dimensional phase space of grain boundaries.« less

  6. Grain boundary plane orientation fundamental zones and structure-property relationships

    SciTech Connect

    Homer, Eric R.; Patala, Srikanth; Priedeman, Jonathan L.

    2015-10-26

    Grain boundary plane orientation is a profoundly important determinant of character in polycrystalline materials that is not well understood. This work demonstrates how boundary plane orientation fundamental zones, which capture the natural crystallographic symmetries of a grain boundary, can be used to establish structure-property relationships. Using the fundamental zone representation, trends in computed energy, excess volume at the grain boundary, and temperature-dependent mobility naturally emerge and show a strong dependence on the boundary plane orientation. Analysis of common misorientation axes even suggests broader trends of grain boundary energy as a function of misorientation angle and plane orientation. Due to the strong structure-property relationships that naturally emerge from this work, boundary plane fundamental zones are expected to simplify analysis of both computational and experimental data. This standardized representation has the potential to significantly accelerate research in the topologically complex and vast five-dimensional phase space of grain boundaries.

  7. Modelling of the structure-property relationships in the α-quartz structures

    NASA Astrophysics Data System (ADS)

    Yao, Yongtao; Alderson, Kim; Alderson, Andrew; Leng, Jinsong

    2013-04-01

    The molecular mechanism has been employed to model the structure-property relationships of auxetic material with tetrahedral framework at the atomistic level. The germania α-quartz subject uniaxial stress loading in z direction will be investigated. The strain-dependent structure and mechanical properties will be predicted from the force field based simulations, including the transformation from positive-to-negative Poisson's ratio behaviour and vice versa.

  8. Structure-Property-Function Relationship in Humic Substances to Explain the Biological Activity in Plants

    PubMed Central

    García, Andrés Calderín; de Souza, Luiz Gilberto Ambrosio; Pereira, Marcos Gervasio; Castro, Rosane Nora; García-Mina, José María; Zonta, Everaldo; Lisboa, Francy Junior Gonçalves; Berbara, Ricardo Luis Louro

    2016-01-01

    Knowledge of the structure-property-function relationship of humic substances (HSs) is key for understanding their role in soil. Despite progress, studies on this topic are still under discussion. We analyzed 37 humic fractions with respect to their isotopic composition, structural characteristics, and properties responsible for stimulating plant root parameters. We showed that regardless of the source of origin of the carbon (C3 or C4), soil-extracted HSs and humic acids (HAs) are structurally similar to each other. The more labile and functionalized HS fraction is responsible for root emission, whereas the more recalcitrant and less functionalized HA fraction is related to root growth. Labile structures promote root stimulation at lower concentrations, while recalcitrant structures require higher concentrations to promote a similar stimulus. These findings show that lability and recalcitrance, which are derived properties of humic fractions, are related to the type and intensity of their bioactivity. In summary, the comparison of humic fractions allowed a better understanding of the relationship between the source of origin of plant carbon and the structure, properties, and type and intensity of the bioactivity of HSs in plants. In this study, scientific concepts are unified and the basis for the agronomic use of HSs is established. PMID:26862010

  9. Structure-Property-Function Relationship in Humic Substances to Explain the Biological Activity in Plants.

    PubMed

    García, Andrés Calderín; de Souza, Luiz Gilberto Ambrosio; Pereira, Marcos Gervasio; Castro, Rosane Nora; García-Mina, José María; Zonta, Everaldo; Lisboa, Francy Junior Gonçalves; Berbara, Ricardo Luis Louro

    2016-01-01

    Knowledge of the structure-property-function relationship of humic substances (HSs) is key for understanding their role in soil. Despite progress, studies on this topic are still under discussion. We analyzed 37 humic fractions with respect to their isotopic composition, structural characteristics, and properties responsible for stimulating plant root parameters. We showed that regardless of the source of origin of the carbon (C3 or C4), soil-extracted HSs and humic acids (HAs) are structurally similar to each other. The more labile and functionalized HS fraction is responsible for root emission, whereas the more recalcitrant and less functionalized HA fraction is related to root growth. Labile structures promote root stimulation at lower concentrations, while recalcitrant structures require higher concentrations to promote a similar stimulus. These findings show that lability and recalcitrance, which are derived properties of humic fractions, are related to the type and intensity of their bioactivity. In summary, the comparison of humic fractions allowed a better understanding of the relationship between the source of origin of plant carbon and the structure, properties, and type and intensity of the bioactivity of HSs in plants. In this study, scientific concepts are unified and the basis for the agronomic use of HSs is established. PMID:26862010

  10. Structure-Property-Function Relationship in Humic Substances to Explain the Biological Activity in Plants

    NASA Astrophysics Data System (ADS)

    García, Andrés Calderín; de Souza, Luiz Gilberto Ambrosio; Pereira, Marcos Gervasio; Castro, Rosane Nora; García-Mina, José María; Zonta, Everaldo; Lisboa, Francy Junior Gonçalves; Berbara, Ricardo Luis Louro

    2016-02-01

    Knowledge of the structure-property-function relationship of humic substances (HSs) is key for understanding their role in soil. Despite progress, studies on this topic are still under discussion. We analyzed 37 humic fractions with respect to their isotopic composition, structural characteristics, and properties responsible for stimulating plant root parameters. We showed that regardless of the source of origin of the carbon (C3 or C4), soil-extracted HSs and humic acids (HAs) are structurally similar to each other. The more labile and functionalized HS fraction is responsible for root emission, whereas the more recalcitrant and less functionalized HA fraction is related to root growth. Labile structures promote root stimulation at lower concentrations, while recalcitrant structures require higher concentrations to promote a similar stimulus. These findings show that lability and recalcitrance, which are derived properties of humic fractions, are related to the type and intensity of their bioactivity. In summary, the comparison of humic fractions allowed a better understanding of the relationship between the source of origin of plant carbon and the structure, properties, and type and intensity of the bioactivity of HSs in plants. In this study, scientific concepts are unified and the basis for the agronomic use of HSs is established.

  11. Structure-property relationships of electron-beam-irradiated monomeric and polymeric systems

    SciTech Connect

    Kim, Ha Chul.

    1989-01-01

    Structure-property relationships were investigated for electron beam (EB) irradiated monomeric and polymeric systems. The objectives were to study the feasibility of preparing systems of potential application, and to characterize these systems in terms of structure-property behavior. In this thesis, the basic theories on radiation chemistry were first reviewed. Next, five different studies on the application of EB radiation were discussed. In the first study on the surface modification of the methacyclic acid derivative of the glycidyl ether of bis-phenol A(bis-GMA) substrates, considerable changes in wetting characteristics were observed using functionalized poly(dimethyl siloxane) (PDMS) oligomers as surface modifiers. The second subject was utilized to cross-linked caprolactone-allyl glycidyl ether(CL-AGE) copolymers. EB radiation was utilized to crosslink these materials at various temperatures both above and below the crystalline melting point. In the third study, models of time-temperature-energy(TTE) diagrams in an idealized EB radiation curing system were developed to help provide a conceptual understanding of the TTE relationship. The fourth study focused on the effects of EB irradiation on the mechanical and thermal properties of poly(phenylene sulfide). In the fifth study, two systems(symmetric and asymmetric) based on the controlled distribution of bis-GMA within a crosslinked nitrile rubber(NBR) network were prepared utilizing EB irradiation.

  12. Structure-property relationships in self-assembling peptide hydrogels, homopolypeptides and polysaccharides

    NASA Astrophysics Data System (ADS)

    Hule, Rohan A.

    The main objective of this dissertation is to investigate quantitative structure-property relationships in a variety of molecular systems including de novo designed peptides, peptide amphiphiles, polysaccharides and high molecular weight polypeptides. Peptide molecules consisting of 20 amino acids were designed to undergo thermally triggered intramolecular folding into asymmetric beta-hairpins and intermolecular self-assembly via a strand swapping mechanism into physically crosslinked fibrillar hydrogels. The self-assembly mechanism was confirmed by multiple characterization techniques such as circular dichroism and FITR spectroscopy, atomic force and transmission electron microscopy and small angle neutron scattering. Three distinct fibrillar nanostructures, i.e. non-twisted, twisted and laminated were produced, depending on the degree of strand asymmetry and peptide registry. Differences in the fibrillar morphology have a direct consequence on the mechanical properties of the hydrogels, with the laminated hydrogels exhibiting a significantly higher elastic modulus as compared to the twisted or non-twisted fibrillar hydrogels. SANS and cryo-TEM data reveal that the self-assembled fibrils form networks that are fractal in nature. Models employed to elucidate the fractal behavior can relate changes in the correlation lengths, low q (network), and high q (fibrillar) fractal exponents to the distinct fibrillar nanomorphology. The fractal dimension of the networks varies significantly, from a mass to a surface fractal and can be directly related to the local fibrillar morphology and changes in the peptide concentration. Transitions in the fractal behavior seen in the high q regime can be attributed to self-assembly kinetics. An identical model can be used to establish a direct correlation between the bulk properties and changes in both, the network density and underlying morphology, of a modified peptide-based hydrogel. As in the case of asymmetric peptides, changes in

  13. Anomalous structure-property relationships in metallic glasses through pressure-mediated glass formation

    NASA Astrophysics Data System (ADS)

    Ding, Jun; Asta, Mark; Ritchie, Robert O.

    2016-04-01

    Metallic glasses are commonly found to favor denser packing structures and icosahedral order in experiments, simulations, and theoretical models. Here we present a molecular dynamics simulation study of Cu-Zr metallic glasses, prepared through a pressure-mediated pathway. The resulting glasses exhibit anomalous structure-property relationships; these glasses are less energetically stable, concomitant with a denser atomic packing and a significant increase in icosahedral short-range order. The enhanced icosahedral order is shown to be accompanied by a pressure-mediated change in chemical short-range order. The results demonstrate that in amorphous alloys (nonmonatomic), theoretical frameworks of the two-order-parameter model must be generalized to account for chemical degrees of freedom.

  14. Polydopamine and eumelanin: from structure-property relationships to a unified tailoring strategy.

    PubMed

    d'Ischia, Marco; Napolitano, Alessandra; Ball, Vincent; Chen, Chun-Teh; Buehler, Markus J

    2014-12-16

    CONSPECTUS: Polydopamine (PDA), a black insoluble biopolymer produced by autoxidation of the catecholamine neurotransmitter dopamine (DA), and synthetic eumelanin polymers modeled to the black functional pigments of human skin, hair, and eyes have burst into the scene of materials science as versatile bioinspired functional systems for a very broad range of applications. PDA is characterized by extraordinary adhesion properties providing efficient and universal surface coating for diverse settings that include drug delivery, microfluidic systems, and water-treatment devices. Synthetic eumelanins from dopa or 5,6-dihydroxyindoles are the focus of increasing interest as UV-absorbing agents, antioxidants, free radical scavengers, and water-dependent hybrid electronic-ionic semiconductors. Because of their peculiar physicochemical properties, eumelanins and PDA hold considerable promise in nanomedicine and bioelectronics, as they are biocompatible, biodegradable, and exhibit suitable mechanical properties for integration with biological tissues. Despite considerable similarities, very few attempts have so far been made to provide an integrated unifying perspective of these two fields of technology-oriented chemical research, and progress toward application has been based more on empirical approaches than on a solid conceptual framework of structure-property relationships. The present Account is an attempt to fill this gap. Following a vis-à-vis of PDA and eumelanin chemistries, it provides an overall view of the various levels of chemical disorder in both systems and draws simple correlations with physicochemical properties based on experimental and computational approaches. The potential of large-scale simulations to capture the macroproperties of eumelanin-like materials and their hierarchical structures, to predict the physicochemical properties of new melanin-inspired materials, to understand the structure-property-function relationships of these materials from

  15. Structure-property relationships in the design, assembly and applications of polyelectrolyte multilayer thin films

    NASA Astrophysics Data System (ADS)

    Rmaile, Hassan H.

    Ultrathin films consisting of an alternating sequence of positively and negatively charged polyelectrolytes have been prepared by means of the electrostatic layer-by-layer sequential assembly technique. To augment their typical applications in the water treatment, personal care as well as the pulp and paper industry, the structure and the design of these polyelectrolytes were tailored synthetically to satisfy the requirements of different types of applications. Some were used for surface modifications, hydrophobic and hydrophilic coatings, corrosion protection, conducting and biocompatible surfaces. Others were found to be very efficient for membrane and chromatographic applications. The ease with which these multilayer coatings can be constructed, their robustness and stability make them very good candidates for industrial applications. The dissertation focuses mainly on the structure-property relationships of these polyelectrolytes and their corresponding thin films. Various polyelectrolytes were synthesized or modified in a strategic approach and gave novel and promising properties. Some of them exhibited permeabilities that were higher than any membranes reported in the literature. Also, some are potentially very useful for designing drug delivery systems such as tablets or encapsulations since they were shown to control the permeability of sample drugs and vitamins very efficiently based on their sensitivity to pH changes. Other synthesized polyelectrolytes proved to be very effective in preventing protein adsorption or promoting cell growth and differentiation. Some systems were very useful as robust stationary phases for simple chiral separations in capillary electrochromatography. Along with modifications and improvements, the approach might one day be applied commercially for chiral separations using high performance liquid chromatography and replace currently used stationary phases. Last but not least, the potential for these polyelectrolytes and their

  16. Structure-property relationships of anionic permselective membranes. [Fe/Cr redox storage batteries

    SciTech Connect

    Arnold, C. Jr.

    1983-01-01

    Anionic exchange membranes are used in Fe/Cr redox storage batteries to separate the anolyte from the catholyte and provide electrical continuity. Membranes with lower area resistivity, higher selectivity and reduced susceptibility toward fouling are required to improve the efficiency and lifetime of these batteries. In order to develop improved membrane, a better understanding of the relationships between these properties and such structural parameters as degree of crosslinking, ion exchange capacity and porosity were needed. The primary objective of this work was to define the structure-property relationships of anionic permselective membranes. A secondary goal was to develop empirical models which can be used to predict membrane performance. This kind of information should be useful for the development of improved membranes. To accomplish these goals a factorial study was carried out with model membranes. These membranes were designed in such a way that all three structural parameters could be varied independently. In this paper it will be shown how this approach not only provided models which could be used to predict membrane performance, but also how one of the model membrane exhibited better properties than state-of-the-art membranes.

  17. Design, synthesis, and structure-property relationships of isoindigo-based conjugated polymers.

    PubMed

    Lei, Ting; Wang, Jie-Yu; Pei, Jian

    2014-04-15

    Conjugated polymers have developed rapidly due to their promising applications in low-cost, lightweight, and flexible electronics. The development of the third-generation donor-acceptor (D-A) polymers greatly improved the device performance in organic solar cells (OSCs) and field-effect transistors (FETs). However, for further improvement of device performance, scientists need to develop new building blocks, in particular electron-deficient aromatics, and gain an in-depth understanding of the structure-property relationships. Recently, isoindigo has been used as a new acceptor of D-A conjugated polymers. An isomer of indigo, isoindigo is a less well-known dye and can be isolated as a by-product from certain biological processes. It has two lactam rings and exhibits strong electron-withdrawing character. This electron deficiency gives isoindigo-based polymers intriguing properties, such as broad absorption and high open circuit voltage in OSCs, as well as high mobility and good ambient stability in FETs. In this Account, we review our recent progress on the design, synthesis, and structure-property relationship study of isoindigo-based polymers for FETs. Starting with some discussion on carrier transport in polymer films, we provide some basic strategies towards high-performance polymer FETs. We discuss the stability issue of devices, the impediment of the alkyl side chains, and the choice of the donor part of conjugated polymers. We demonstrate that introducing the isoindigo core effectively lowers the HOMO levels of polymers and provides FETs with long-time stability. In addition, we have found that when we use inappropriate alkyl side chains or non-centrosymmetric donors, the device performance of isoindigo polymers suffers. To further improve device performance and ambient stability, we propose several design strategies, such as using farther branched alkyl chains, modulating polymer energy levels, and extending π-conjugated backbones. We have found that using

  18. Localized surface plasmon resonance induced structure-property relationships of metal nanostructures

    NASA Astrophysics Data System (ADS)

    Vilayurganapathy, Subramanian

    The confluence of nanotechnology and plasmonics has led to new and interesting phenomena. The industrial need for fast, efficient and miniature devices which constantly push the boundaries on device performance tap into the happy marriage between these diverse fields. Designing devices for real life application that give superior performance when compared with existing ones are enabled by a better understanding of their structure-property relationships. Among all the design constraints, without doubt, the shape and size of the nanostructure along with the dielectric medium surrounding it has the maximum influence on the response and thereby the performance of the device. Hence a careful study of the above mentioned parameters is of utmost importance in designing efficient devices. In this dissertation, we synthesize and study the optical properties of nanostructures of different shapes and size. In particular, we estimated the plasmonic near field enhancement via surface-enhanced Raman scattering (SERS) and 2-photon Photoemission electron microscopy (2P-PEEM). We synthesized the nanostructures using four different techniques. One synthesis technique, the thermal growth method was employed to grow interesting Ag and Au nanostructures on Si. The absence of toxic chemicals during nanostructure synthesis via the thermal growth technique opens up myriad possibilities for applications in the fields of biomedical science, bioengineering, drug delivery among others along with the huge advantage of being environment friendly. The other three synthesis techniques (ion implantation, Electrodeposition and FIB lithography) were chosen with the specific goal of designing novel plasmonic metal, metal hybrid nanostructures as photocathode materials in next generation light sources. The synthesis techniques for these novel nanostructures were dictated by the requirement of high quantum efficiency, robustness under constant irradiation and coherent unidirectional electron emission

  19. Probing Structure Property Relationships in Complex Engineering Silicones by 1H NMR

    SciTech Connect

    Chinn, S C; Gjersing, E L; Maxwell, R S; Eastwood, E; Bowen, D; Stephens, T

    2006-07-14

    It is generally accepted that the properties of polymeric materials are controlled by the network structure and the reactions by which they have been constructed. These properties include the bulk moduli at creation, but also the properties as a function of age during use. In order to interpret mechanical properties and predict the time dependent changes in these properties, detailed knowledge of the effect of structural changes must be obtained. The degree and type of crosslinking, the molecular weight between crosslinks, the number of elastically ineffective chains (loops, dangling chain ends, sol-fraction) must be characterized. A number of theoretical and experimental efforts have been reported in the last few years on model networks prepared by endlinking reactions and the relationships of those structures with the ultimate mechanical properties. A range of experimental methods have been used to investigate structure including rheometric, scattering, infrared, {sup 29}Si MAS and CPMAS, {sup 1}H relaxation measurements, and recently {sup 1}H multiple quantum methods. Characterization of the growth of multiple quantum coherences have recently been shown to provide detailed insight into silicone network structure by the ability to selective probe the individual components of the polymer network, such as the polymer-filler interface or network chains. We have employed recently developed MQ methods to investigate the structure-property relationships in a series of complex, endlinked filled-PDMS blends. Here, a systematic study of the relationship between the molecular formulation, as dictated by the amount and type of crosslinks present and by the remaining network chains, and the segmental dynamics as observed by MQ NMR was performed.

  20. Structure/property relationships in polymer membranes for water purification and energy applications

    NASA Astrophysics Data System (ADS)

    Geise, Geoffrey

    Providing sustainable supplies of purified water and energy is a critical global challenge for the future, and polymer membranes will play a key role in addressing these clear and pressing global needs for water and energy. Polymer membrane-based processes dominate the desalination market, and polymer membranes are crucial components in several rapidly developing power generation and storage applications that rely on membranes to control rates of water and/or ion transport. Much remains unknown about the influence of polymer structure on intrinsic water and ion transport properties, and these relationships must be developed to design next generation polymer membrane materials. For desalination applications, polymers with simultaneously high water permeability and low salt permeability are desirable in order to prepare selective membranes that can efficiently desalinate water, and a tradeoff relationship between water/salt selectivity and water permeability suggests that attempts to prepare such materials should rely on approaches that do more than simply vary polymer free volume. One strategy is to functionalize hydrocarbon polymers with fixed charge groups that can ionize upon exposure to water, and the presence of charged groups in the polymer influences transport properties. Additionally, in many emerging energy applications, charged polymers are exposed to ions that are very different from sodium and chloride. Specific ion effects have been observed in charged polymers, and these effects must be understood to prepare charged polymers that will enable emerging energy technologies. This presentation discusses research aimed at further understanding fundamental structure/property relationships that govern water and ion transport in charged polymer films considered for desalination and electric potential field-driven applications that can help address global needs for clean water and energy.

  1. Quantitative relationships in delphinid neocortex

    PubMed Central

    Mortensen, Heidi S.; Pakkenberg, Bente; Dam, Maria; Dietz, Rune; Sonne, Christian; Mikkelsen, Bjarni; Eriksen, Nina

    2014-01-01

    Possessing large brains and complex behavioral patterns, cetaceans are believed to be highly intelligent. Their brains, which are the largest in the Animal Kingdom and have enormous gyrification compared with terrestrial mammals, have long been of scientific interest. Few studies, however, report total number of brain cells in cetaceans, and even fewer have used unbiased counting methods. In this study, using stereological methods, we estimated the total number of cells in the neocortex of the long-finned pilot whale (Globicephala melas) brain. For the first time, we show that a species of dolphin has more neocortical neurons than any mammal studied to date including humans. These cell numbers are compared across various mammals with different brain sizes, and the function of possessing many neurons is discussed. We found that the long-finned pilot whale neocortex has approximately 37.2 × 109 neurons, which is almost twice as many as humans, and 127 × 109 glial cells. Thus, the absolute number of neurons in the human neocortex is not correlated with the superior cognitive abilities of humans (at least compared to cetaceans) as has previously been hypothesized. However, as neuron density in long-finned pilot whales is lower than that in humans, their higher cell number appears to be due to their larger brain. Accordingly, our findings make an important contribution to the ongoing debate over quantitative relationships in the mammalian brain. PMID:25505387

  2. Quantitative relationships in delphinid neocortex.

    PubMed

    Mortensen, Heidi S; Pakkenberg, Bente; Dam, Maria; Dietz, Rune; Sonne, Christian; Mikkelsen, Bjarni; Eriksen, Nina

    2014-01-01

    Possessing large brains and complex behavioral patterns, cetaceans are believed to be highly intelligent. Their brains, which are the largest in the Animal Kingdom and have enormous gyrification compared with terrestrial mammals, have long been of scientific interest. Few studies, however, report total number of brain cells in cetaceans, and even fewer have used unbiased counting methods. In this study, using stereological methods, we estimated the total number of cells in the neocortex of the long-finned pilot whale (Globicephala melas) brain. For the first time, we show that a species of dolphin has more neocortical neurons than any mammal studied to date including humans. These cell numbers are compared across various mammals with different brain sizes, and the function of possessing many neurons is discussed. We found that the long-finned pilot whale neocortex has approximately 37.2 × 10(9) neurons, which is almost twice as many as humans, and 127 × 10(9) glial cells. Thus, the absolute number of neurons in the human neocortex is not correlated with the superior cognitive abilities of humans (at least compared to cetaceans) as has previously been hypothesized. However, as neuron density in long-finned pilot whales is lower than that in humans, their higher cell number appears to be due to their larger brain. Accordingly, our findings make an important contribution to the ongoing debate over quantitative relationships in the mammalian brain. PMID:25505387

  3. Structure property relationships in a nanoparticle-free SmBCO coated conductor

    NASA Astrophysics Data System (ADS)

    Knibbe, R.; Strickland, N. M.; Wimbush, S. C.; Puichaud, A.-H.; Long, N. J.

    2016-06-01

    We examine the temperature, field and field angle dependence of the critical current of a SmBa2Cu3O y coated conductor produced by reactive co-evaporation. A transmission electron microscopy based microstructural analysis shows the film contains extended c-axis defects, stacking faults, and two different species of inclined defects. By applying a maximum entropy decomposition of the field angle dependent critical current I c(θ) datasets we are able to identify the individual contributions of these defects to the critical current even though they do not produce distinct peaks but rather an anisotropy in I c(θ). We are able to confirm the structure property relationships by determining the matching fields where each of the individual defect contributions are a maximum and showing that these are consistent with the observed microstructure. For a critical current component having a maximum magnitude at an intermediate temperature we propose a model of thermally activated depinning to explain the behaviour.

  4. Structure-property relationships of small bandgap conjugated polymers for solar cells.

    PubMed

    Hellström, Stefan; Zhang, Fengling; Inganäs, Olle; Andersson, Mats R

    2009-12-01

    Conjugated polymers as electron donors in solar cells based on donor/acceptor combinations are of great interest, partly due to the possibility of converting solar light with a low materials budget. Six small bandgap polymers with optical bandgap ranging from 1.0-1.9 eV are presented in this paper. All polymers utilize an electron donor-acceptor-donor (DAD) segment in the polymer backbone, creating a partial charge-transfer, to decrease the bandgap. The design, synthesis and the optical characteristics as well as the solar cell characteristics of the polymers are discussed. The positions of the energy levels of the conjugated polymer relative to the electron acceptor are of significant importance and determine not only the driving force for exciton dissociation but also the maximum open-circuit voltage. This work also focuses on investigating the redox behavior of the described conjugated polymers and electron acceptors using square wave voltammetry. Comparing the electrochemical data gives important information of the structure-property relationships of the polymers. PMID:19904430

  5. Probing structure-property relationships in perpendicularly magnetized Fe/Cu(001) using MXLD and XPD

    SciTech Connect

    Cummins, T.R.; Waddill, G.D.; Goodman, K.W.

    1997-04-01

    Magnetic X-ray Linear Dichroism (MXLD) in Photoelectron Spectroscopy and X-Ray Photoelectron Diffraction (XPD) of the Fe 3p core level have been used to probe the magnetic structure-property relationships of perpendicularly magnetized Fe/Cu(001), in an element-specific fashion. A strong MEXLD effect was observed in the high resolution photoelectron spectroscopy of the Fe 3p at {open_quotes}normal{close_quotes} emission and was used to follow the loss of perpendicular ferromagnetic ordering as the temperature was raised toward room temperature. In parallel with this, {open_quotes}Forward Focussing{close_quotes} in XPD was used as a direct measure of geometric structure in the overlayer. These results and the implications of their correlation will be discussed. Additionally, an investigation of the effect of Mn doping of the Fe/Cu(001) will be described. These measurements were performed at the Spectromicroscopy Facility (Beamline 7.0.1) of the Advanced Light Source.

  6. Processing-Structure-Property Relationships in Laser-Annealed PbSe Nanocrystal Thin Films.

    PubMed

    Treml, Benjamin E; Robbins, Andrew B; Whitham, Kevin; Smilgies, Detlef-M; Thompson, Michael O; Hanrath, Tobias

    2015-01-01

    As nanocrystal (NC) synthesis techniques and device architectures advance, it becomes increasingly apparent that new ways of connecting NCs with each other and their external environment are required to realize their considerable potential. Enhancing inter-NC coupling by thermal annealing has been a long-standing challenge. Conventional thermal annealing approaches are limited by the challenge of annealing the NC at sufficiently high temperatures to remove surface-bound ligands while at the same time limiting the thermal budget to prevent large-scale aggregation. Here we investigate nonequilibrium laser annealing of NC thin films that enables separation of the kinetic and thermodynamic aspects of nanocrystal fusion. We show that laser annealing of NC assemblies on nano- to microsecond time scales can transform initially isolated NCs in a thin film into an interconnected structure in which proximate dots "just touch". We investigate both pulsed laser annealing and laser spike annealing and show that both annealing methods can produce "confined-but-connected" nanocrystal films. We develop a thermal transport model to rationalize the differences in resulting film morphologies. Finally we show that the insights gained from study of nanocrystal mono- and bilayers can be extended to three-dimensional NC films. The basic processing-structure-property relationships established in this work provide guidance to future advances in creating functional thin films in which constituent NCs can purposefully interact. PMID:25787088

  7. Structure-property relationships of BaCeO perovskites for the oxidative dehydrogenation of alkanes

    SciTech Connect

    Nenoff, T.M.; Jackson, N.B.; Miller, J.E.; Sault, A.G.; Trudell, D.

    1997-12-01

    The oxidative dehydrogenation (ODH) reactions for the formation of two important organic feedstocks ethylene and propylene are of great interest because of the potential in capital and energy savings associated with these reactions. Theoretically, ODH can achieve high conversions of the starting materials (ethane and propane) at lower temperatures than conventional dehydrogenation reactions. The important focus in this study of ODH catalysts is the development of a structure-property relationship for catalyst with respect to selectivity, so as to avoid the more thermodynamically favorable combustion reaction. Catalysts for the ODH reaction generally consist of mixed metal oxides. Since for the most selective catalyst lattice oxygen is known to participate in the reaction, catalysts are sought with surface oxygen atoms that are labile enough to perform dehydrogenation, but not so plentiful or weakly bound as to promote complete combustion. Also, catalysts must be able to replenish surface oxygen by transport from the bulk. Perovskite materials are candidates to fulfill these requirements. The authors are studying BaCeO{sub 3} perovskites doped with elements such as Ca, Mg, and Sr. During the ODH of the alkanes at high temperatures, the perovskite structure is not retained and a mixture of carbonates and oxides is formed, as revealed by XRD. While the Ca doped materials showed enhanced total combustion activity below 600 C, they only showed enhanced alkene production at 700 C. Bulk structural and surface changes, as monitored by powder X-ray diffraction, and X-ray photoelectron spectroscopy are being correlated with activity in order to understand the factors affecting catalyst performance, and to modify catalyst formulations to improve conversion and selectivity.

  8. Structure-property relationship of quinuclidinium surfactants--Towards multifunctional biologically active molecules.

    PubMed

    Skočibušić, Mirjana; Odžak, Renata; Štefanić, Zoran; Križić, Ivana; Krišto, Lucija; Jović, Ozren; Hrenar, Tomica; Primožič, Ines; Jurašin, Darija

    2016-04-01

    Motivated by diverse biological and pharmacological activity of quinuclidine and oxime compounds we have synthesized and characterized novel class of surfactants, 3-hydroxyimino quinuclidinium bromides with different alkyl chains lengths (CnQNOH; n=12, 14 and 16). The incorporation of non conventional hydroxyimino quinuclidinium headgroup and variation in alkyl chain length affects hydrophilic-hydrophobic balance of surfactant molecule and thereby physicochemical properties important for its application. Therefore, newly synthesized surfactants were characterized by the combination of different experimental techniques: X-ray analysis, potentiometry, electrical conductivity, surface tension and dynamic light scattering measurements, as well as antimicrobial susceptibility tests. Comprehensive investigation of CnQNOH surfactants enabled insight into structure-property relationship i.e., way in which the arrangement of surfactant molecules in the crystal phase correlates with their solution behavior and biologically activity. The synthesized CnQNOH surfactants exhibited high adsorption efficiency and relatively low critical micelle concentrations. In addition, all investigated compounds showed very potent and promising activity against Gram-positive and clinically relevant Gram-negative bacterial strains compared to conventional antimicrobial agents: tetracycline and gentamicin. The overall results indicate that bicyclic headgroup with oxime moiety, which affects both hydrophilicity and hydrophobicity of CnQNOH molecule in addition to enabling hydrogen bonding, has dominant effect on crystal packing and physicochemical properties. The unique structural features of cationic surfactants with hydroxyimino quinuclidine headgroup along with diverse biological activity have made them promising structures in novel drug discovery. Obtained fundamental understanding how combination of different functionalities in a single surfactant molecule affects its physicochemical

  9. Hybrid Mixed Media Nonwovens: An Investigation of Structure-Property Relationships

    NASA Astrophysics Data System (ADS)

    Hollowell, Kendall Birckhead

    There have been myriad studies on utilizing bicomponent splittables produced through spunbond/spunlace processes. These production methods have proven to yield microfibers which increase the surface area of the nonwoven structures. There has been recent focus on studying the microfibers within these nonwoven structures as well as using a multiplicity of deniers of fibers within the nonwoven. There have also been studies on producing nonwovens with fibers of differing cross-sectional shapes and diameters. The purpose of this study is to examine the properties of a nonwoven structure, marrying the concepts of multi-denier fibers with multi-shaped fibers in two configurations: three-layer and alternating. The basis for this study will be US Patent 6,964,931 B2 "Method of making Continuous Filament Web with Statistical Filament Distribution" as well as US Patent 7,981,336 B2 "Process of Making Mixed Fibers and Nonwoven Fabrics". This study addresses the melt-spinning and hydroentanglement of nonwoven webs made from bicomponent fibers in three-layer and alternating configurations. The bicomponent cross-sections that will be used include 16-segmented pie and 7-islands-in-the-sea. In this study the establishment of the utility of mixed media nonwovens will take place through property and structure analysis in order to determine the inherent properties of the mixed media structures as well as the structure-property relationships of the nonwoven fabric. Property and structure analysis will also take place on mixed media structures containing poly(lactic acid) as a sacrificial component in the bicomponent fiber after optimizing the removal conditions of the poly(lactic acid) in a sodium hydroxide (NaOH) bath.

  10. Understanding Structure-Property Relationships for Palladium-Gold Nanoparticles as Colloidal Catalysts

    NASA Astrophysics Data System (ADS)

    Fang, Yu-Lun

    Bimetallic palladium-gold (PdAu) nanoparticle (NP) catalysts have been demonstrated for the better catalytic performance than monometallic Pd catalysts in various reactions; however, the enhancement mechanism is not completely clear for most reactions. This thesis addresses the investigation of PdAu NP catalysts with emphasis on the structure-property relationships in water-phase reactions, using hydrodechlorination (HDC) of trichloroethene (TCE) as the model reaction. Catalyzed TCE HDC is a potential approach for water pollution control, in which colloidal Pd-decorated Au NPs (Pd/Au NPs) are known to be significantly better catalysts than monometallic Pd ones. X-ray absorption spectroscopy (XAS) of carbon-supported Pd/Au NPs with different surface Pd coverages verified their core-shell structure (Au-rich core and Pd-rich shell). Structure evolution was observed upon heat treatment, in which Pd was in the form of surface Pd ensembles at room temperature. The metals formed a surface PdAu alloy or a bulk PdAu alloy above 200°C, as determined from the average coordination environment. Results suggested a new way to promote Pd catalysis, namely, by impregnating supported Pd catalysts with gold salt followed by thermal annealing; such post-impregnation with different heat treatments could lead to >15-fold increase in TCE HDC activity. Pd ensembles on the Au NP surface were demonstrated to be major active sites for TCE HDC as the reaction rates correlated strongly with the size of Pd ensembles determined from XAS. The geometric effect, in which atomic ensembles act as active sites, appeared to dominate over the mixed metal site effect and the electronic effect. Au NPs could stabilize surface Pd atoms in the metallic form, possibly leading to a set of highly active sites that is not present in monometallic Pd NPs. The TCE HDC reaction with Pd/Au NPs and Pd NPs was conducted as a closed batch system. Mass transfer effects in this three-phase reaction were assessed and

  11. The Structure-property Relationships of D-π-A BODIPY Dyes for Dye-sensitized Solar Cells.

    PubMed

    Mao, Mao; Song, Qin-Hua

    2016-04-01

    BODIPY dyes have attracted considerable attention as potential photosensitizers in dye-sensitized solar cells (DSSCs) owing to their excellent optical properties and facile structural modification. This account focuses on recent advances in the molecular design of D-π-A BODIPY dyes for applications in DSSCs. Special attention has been paid to the structure-property relationships of D-π-A BODIPY dyes for DSSCs. The developmental process in the modified position at the BODIPY core with a donor/acceptor is described. The devices based on 2,6-modified BODIPY dyes exhibit better photovoltaic performance over other modified BODIPY dyes. Meanwhile, the research reveals the correlation of molecular structures (various donor chromophores, extended units, molecular frameworks, and long alkyl groups) with their photophysical and electrochemical properties and relates it to their performance in DSSCs. The structure-property relationships give valuable information and guidelines for designing new D-π-A BODIPY dyes for DSSCs. PMID:26846846

  12. Land-use and land-management change: relationships with earthworm and fungi communities and soil structural properties

    PubMed Central

    2013-01-01

    Background Change in land use and management can impact massively on soil ecosystems. Ecosystem engineers and other functional biodiversity in soils can be influenced directly by such change and this in turn can affect key soil functions. Here, we employ meta-analysis to provide a quantitative assessment of the effects of changes in land use and land management across a range of successional/extensification transitions (conventional arable → no or reduced tillage → grassland → wooded land) on community metrics for two functionally important soil taxa, earthworms and fungi. An analysis of the relationships between community change and soil structural properties was also included. Results Meta-analysis highlighted a consistent trend of increased earthworm and fungal community abundances and complexity following transitions to lower intensity and later successional land uses. The greatest changes were seen for early stage transitions, such as introduction of reduced tillage regimes and conversion to grassland from arable land. Not all changes, however, result in positive effects on the assessed community metrics. For example, whether woodland conversion positively or negatively affects community size and complexity depends on woodland type and, potentially, the changes in soil properties, such as pH, that may occur during conversion. Alterations in soil communities tended to facilitate subsequent changes in soil structure and hydrology. For example, increasing earthworm abundances and functional group composition were shown to be positively correlated with water infiltration rate (dependent on tillage regime and habitat characteristics); while positive changes in fungal biomass measures were positively associated with soil microaggregate stability. Conclusions These findings raise the potential to manage landscapes to increase ecosystem service provision from soil biota in relation to regulation of soil structure and water flow. PMID:24289220

  13. Chemical Modification and Structure-property Relationships of Acrylic and Ionomeric Thermoplastic Elastomer Gels

    NASA Astrophysics Data System (ADS)

    Vargantwar, Pruthesh Hariharrao

    Block copolymers (BCs) have remained at the forefront of materials research due to their versatility in applications ranging from hot-melt/pressure-sensitive adhesives and impact modifiers to compatibilizing agents and vibration-dampening/nanotemplating media. Of particular interest are macromolecules composed of two or more chemically dissimilar blocks covalently linked together to form triblock or pentablock copolymers. If the blocks are sufficiently incompatible and the copolymer behaves as a thermoplastic elastomer, the molecules can spontaneously self-assemble to form nanostructured materials that exhibit shape memory due to the formation of a supramolecular network. The BCs of these types are termed as conventional. When BCs contain blocks having ionic moieties such as sulfonic acid groups, they are termed as block ionomers. Designing new systems based on either conventional or ionic BCs, characterizing their structure-property relationships and later using them as electroacive polymers form the essential objectives of this work. Electroactive polymers (EAPs) exhibit electromechanical actuation when stimulated by an external electric field. In the first part of this work, it is shown that BCs resolve some of the outstanding problems presently encountered in the design of two different classes of EAP actuators: dielectric elastomers (DEs) and ionic polymer metal composites (IPMCs). All-acrylic triblock copolymer gels used as DEs actuate with high efficacy without any requirement of mechanical prestrain and, thus, eliminate the need for bulky and heavy hardware essential with prestrained dielectric actuators, as well as material problems associated with stress relaxation. The dependence of actuation behavior on gel morphology as evaluated from mechanical and microstructure studies is observed. In the case of IPMCs, ionic BCs employed in this study greatly facilitate processing compared to other contenders such as NafionRTM, which is commonly used in this class

  14. Structure-property-performance relationships of new high temperature relaxors for capacitor applications

    NASA Astrophysics Data System (ADS)

    Stringer, Craig J.

    temperature (Tf) of ˜150°C. Static and in-situ transmission electron microscopy investigations of the BS-PMN-PT compositions demonstrated a frustrated microstructure of nanometer scale regions and were used to establish structure-property relationships with different electric field and thermal histories. A comparative study of the key relaxor parameters, EA, T f, and TD was tabulated with previously investigated relaxor ferroelectrics. These parameters were found to scale relative to other lead-based perovskite relaxor ferroelectric compounds and solid solutions, with the BS-PMN-PT ternary system exhibiting the highest temperature behavior. Finally, to demonstrate one possible application area for these materials, multilayer ceramic capacitor devices were designed for operation at 300°C and up to 10 kHz. The voltage saturation was found to be extremely encouraging at 300°C with observed changes in capacitance (˜3%) on the application of 10 kV/cm. The insulation resistivity followed an Arrhenius behavior and at 300°C was ˜1010 O-cm. Weibull statistics were used to estimate a characteristic breakdown field at 300°C for the BS-PMN-PT multilayer capacitors of ˜40 kV/cm. Current-voltage measurements were performed to voltages up to breakdown and exhibited Ohmic behavior, indicating intrinsically controlled conduction. Highly accelerated life time tests were performed on BS-PMN-PT capacitors. It was observed that silver migration from termination electrodes caused premature failure at elevated temperature.

  15. Structure-property relationships in halogenbenzoic acids: Thermodynamics of sublimation, fusion, vaporization and solubility.

    PubMed

    Zherikova, Kseniya V; Svetlov, Aleksey A; Kuratieva, Natalia V; Verevkin, Sergey P

    2016-10-01

    Temperature dependences of vapor pressures for 2-, 3-, and 4-bromobenzoic acid, as well as for five isomeric bromo-methylbenzoic acids were studied by the transpiration method. Melting temperatures and enthalpies of fusion for all isomeric bromo-methylbenzoic acids and 4-bromobenzoic acid were measured with a DSC. The molar enthalpies of sublimation and vaporization were derived. These data together with results available in the literature were collected and checked for internal consistency using a group-additivity procedure and results from X-ray structural diffraction studies. Specific (hydrogen bonding) interactions in the liquid and in the crystal phase of halogenbenzoic acids were quantified based on experimental values of vaporization and sublimation enthalpies. Structure-property correlations of solubilities of halogenobenzoic acids with sublimation pressures and sublimation enthalpies were developed and solubilities of bromo-benzoic acids were estimated. These new results resolve much of the ambiguity in the available thermochemical and solubility data on bromobenzoic acids. The approach based on structure property correlations can be applied for the assessment of water solubility of sparingly soluble drugs. PMID:27424058

  16. Development of quantitative structure-pharmacokinetic relationships.

    PubMed Central

    Mayer, J M; van de Waterbeemd, H

    1985-01-01

    Quantitative structure-activity relationships (QSAR) relating biological activity to physiochemical descriptors have been successfully used for a number of years. It is also long recognized that pharmacokinetic parameters may play an important and even determinant role in drug action. This prompted several researchers to focus attention to pharmacokinetic parameters as potential descriptors in quantitative drug design. A number of examples of quantitative structure-pharmacokinetic relationships (QSPR) have appeared in the literature. The present contribution reviews some developments in this field. In particular, a number of concepts and problems are critically discussed, rather than compilations of examples already published in recent reviews. Attention will be paid to the main processes of the pharmacokinetic or toxicokinetic phase in drug action, including absorption, distribution and elimination (biotransformation and excretion). It is clear that quantitative approaches are of considerable interest to toxicologists, since these methods may contribute to the development of real predictive toxicology. PMID:3905378

  17. Quantitative structure-hydrophobicity relationships of molecular fragments and beyond.

    PubMed

    Zou, Jian-Wei; Huang, Meilan; Huang, Jian-Xiang; Hu, Gui-Xiang; Jiang, Yong-Jun

    2016-03-01

    Quantitative structure-property relationship (QSPR) models were firstly established for the hydrophobic substituent constant (πX) using the theoretical descriptors derived solely from electrostatic potentials (EPSs) at the substituent atoms. The descriptors introduced are found to be related to hydrogen-bond basicity, hydrogen-bond acidity, cavity, or dipolarity/polarizability terms in linear solvation energy relationship, which endows the models good interpretability. The predictive capabilities of the models constructed were also verified by rigorous Monte Carlo cross-validation. Then, eight groups of meta- or para-disubstituted benzenes and one group of substituted pyridines were investigated. QSPR models for individual systems were achieved with the ESP-derived descriptors. Additionally, two QSPR models were also established for Rekker's fragment constants (foct), which is a secondary-treatment quantity and reflects average contribution of the fragment to logP. It has been demonstrated that the descriptors derived from ESPs at the fragments, can be well used to quantitatively express the relationship between fragment structures and their hydrophobic properties, regardless of the attached parent structure or the valence state. Finally, the relations of Hammett σ constant and ESP quantities were explored. It implies that σ and π, which are essential in classic QSAR and represent different type of contributions to biological activities, are also complementary in interaction site. PMID:26826800

  18. Structure-Property Relationships of Polymer Brushes in Restricted Geometries and their Utilization as Ultra-Low Lubricants

    SciTech Connect

    Kuhl, Tonya Lynn; Faller, Roland

    2015-09-28

    Though polymer films are widely used to modify or tailor the physical, chemical and mechanical properties of interfaces in both solid and liquid systems, the rational design of interface- or surface-active polymer modifiers has been hampered by a lack of information about the behavior and structure-property relationships of this class of molecules. This is especially true for systems in which the role of the polymer is to modify the interaction between two solid surfaces in intimate contact and under load, to cause them to be mechanically coupled (e.g. to promote adhesion and wetting) or to minimize their interaction (e.g. lubrication, colloidal stabilization, etc.). Detailed structural information on these systems has largely been precluded by the many difficulties and challenges associated with direct experimental measurements of polymer structure in these geometries. As a result, many practitioners have been forced to employ indirect measurements or rely wholly on theoretical modeling. This has resulted in an incomplete understanding of the structure-property relationships, which are relied upon for the rational design of improved polymer modifiers. Over the course of this current research program, we made direct measurements of the structure of polymers at the interface between two solid surfaces under confinement and elucidated the fundamental physics behind these phenomena using atomistic and coarse grained simulations. The research has potential to lead to new lubricants and wear reducing agents to improve efficiency.

  19. A Summative Report on Exploring Quantitative Relationships

    ERIC Educational Resources Information Center

    Carl, Minette; Goldberg, Robert; Waxman, Jerry

    2004-01-01

    During the years 2000-2003, a course on Exploring Quantitative Relationships (EQR) was created at Queens College under the support of the U.S. Department of Education Fund for the Improvement of Post-Secondary Education (DOE-FIPSE Grant No. P116B000772). Exploratory in nature, the course goals were to acquaint liberal arts students with…

  20. Structure-property relationships in multilayered polymeric system and olefinic block copolymers

    NASA Astrophysics Data System (ADS)

    Khariwala, Devang

    Chapter 1. The effect of tie-layer thickness on delamination behavior of polypropylene/tie-layer/Nylon-6 multilayers is examined in this study. Various maleated polypropylene resins were compared for their effectiveness as tie-layers. Delamination failure occurred cohesively in all the multilayer systems. Two adhesion regimes were defined based on the change in slope of the linear relationship between the delamination toughness and the tie-layer thickness. The measured delamination toughness of the various tie-layers was quantitatively correlated to the damage zone length formed at the crack tip. In addition, the effect of tie-layer thickness on the multilayer tensile properties was correlated with the delamination behavior. The fracture strain of the multilayers decreased with decreasing tie-layer thickness. Examination of the prefracture damage mechanism of stretched multilayers revealed good correlation with the delamination toughness of the tie-layers. In thick tie-layers (>2microm) the delamination toughness of the tie-layers was large enough to prevent delamination of multilayers when they were stretched. In the thin tie-layers (<2microm) the delamination toughness of all the tie-layers is low and consequently delamination led to premature fracture in stretched multilayers. Chapter 2. The kinetics of interdiffusion in the layer multiplying coextrusion process was studied between the miscible Nylon-6 and EVOH pair. The interdiffusion was followed by studying multilayer films of alternating Nylon-6 and EVOH layers that were coextruded with increasing number of layers. The AFM confirmed that the layers interdiffused with increasing number of layers and were forced to a homogeneous blend after several multiplications. The oxygen permeability of Nylon-6/EVOH multilayers was strongly affected by the amount of interdiffusion. The symmetry of the multilayers made it possible to model the composition profile through the layer thickness by application of Fick's law of

  1. Understanding nanocellulose chirality and structure-properties relationship at the single fibril level

    NASA Astrophysics Data System (ADS)

    Usov, Ivan; Nyström, Gustav; Adamcik, Jozef; Handschin, Stephan; Schütz, Christina; Fall, Andreas; Bergström, Lennart; Mezzenga, Raffaele

    2015-06-01

    Nanocellulose fibrils are ubiquitous in nature and nanotechnologies but their mesoscopic structural assembly is not yet fully understood. Here we study the structural features of rod-like cellulose nanoparticles on a single particle level, by applying statistical polymer physics concepts on electron and atomic force microscopy images, and we assess their physical properties via quantitative nanomechanical mapping. We show evidence of right-handed chirality, observed on both bundles and on single fibrils. Statistical analysis of contours from microscopy images shows a non-Gaussian kink angle distribution. This is inconsistent with a structure consisting of alternating amorphous and crystalline domains along the contour and supports process-induced kink formation. The intrinsic mechanical properties of nanocellulose are extracted from nanoindentation and persistence length method for transversal and longitudinal directions, respectively. The structural analysis is pushed to the level of single cellulose polymer chains, and their smallest associated unit with a proposed 2 × 2 chain-packing arrangement.

  2. Understanding nanocellulose chirality and structure-properties relationship at the single fibril level.

    PubMed

    Usov, Ivan; Nyström, Gustav; Adamcik, Jozef; Handschin, Stephan; Schütz, Christina; Fall, Andreas; Bergström, Lennart; Mezzenga, Raffaele

    2015-01-01

    Nanocellulose fibrils are ubiquitous in nature and nanotechnologies but their mesoscopic structural assembly is not yet fully understood. Here we study the structural features of rod-like cellulose nanoparticles on a single particle level, by applying statistical polymer physics concepts on electron and atomic force microscopy images, and we assess their physical properties via quantitative nanomechanical mapping. We show evidence of right-handed chirality, observed on both bundles and on single fibrils. Statistical analysis of contours from microscopy images shows a non-Gaussian kink angle distribution. This is inconsistent with a structure consisting of alternating amorphous and crystalline domains along the contour and supports process-induced kink formation. The intrinsic mechanical properties of nanocellulose are extracted from nanoindentation and persistence length method for transversal and longitudinal directions, respectively. The structural analysis is pushed to the level of single cellulose polymer chains, and their smallest associated unit with a proposed 2 × 2 chain-packing arrangement. PMID:26108282

  3. Solvent effects on the structure-property relationship of anticonvulsant hydantoin derivatives: A solvatochromic analysis.

    PubMed

    Trišović, Nemanja; Valentić, Nataša; Ušćumlić, Gordana

    2011-01-01

    Considering the pharmaceutical importance of hydantoins, a set of 25 derivatives of phenytoin, nirvanol and 5-methyl-5-phenylhydantoin, the lipophilicities of which were gradually increased by the introduction of different alkyl, cycloalkyl and alkenyl groups in position N3, was synthesized. Their properties under consideration were either estimated empirically, by UV/Vis spectroscopy, or calculated using established medicinal chemistry software. The UV absorption spectra of the investigated compounds were recorded in the region from 200 to 400 nm, in selected solvents of different polarities. The effects of solvent dipolarity/polarizability and solvent-solute hydrogen bonding interactions were analyzed by means of the linear solvation energy relationship (LSER) concept proposed by Kamlet and Taft. Furthermore, the relationships between solvent-solute interactions and selected structural features of the solutes, which are believed to markedly affect the processes of absorption, distribution, metabolism, excretion and toxicity (ADMETox), were discussed. Satisfactory correlations were found between hydrogen bonding properties and solute size and the in silico calculated bioactivity descriptors, in particular %Abs. (human intestinal absorption), log BB (blood-brain barrier permeation) and log kA (protein binding affinities) parameters. In view of the results of this study, the investigated hydantoin derivatives met the pharmacokinetic criteria for pre-selection as drug candidates and qualified them for the pharmacodynamic phase of antiepileptic drug development. PMID:21999701

  4. Study of Chemistry and Structure-Property Relationship on Tunable Plasmonic Nanostructures

    NASA Astrophysics Data System (ADS)

    Jing, Hao

    In this dissertation, the rational design and controllable fabrication of an array of novel plasmonic nanostructures with geometrically tunable optical properties are demonstrated, including metal-semiconductor hybrid hetero-nanoparticles, bimetallic noble metal nanoparticles and hollow nanostructures (nanobox and nanocage). Firstly, I have developed a robust wet chemistry approach to the geometry control of Ag-Cu2O core-shell nanoparticles through epitaxial growth of Cu2O nanoshells on the surfaces of various Ag nanostructures, such as quasi-spherical nanoparticles, nanocubes, and nanocuboids. Precise control over the core and the shell geometries enables me to develop detailed, quantitative understanding of how the Cu2O nanoshells introduce interesting modifications to the resonance frequencies and the extinction spectral line shapes of multiple plasmon modes of the Ag cores. Secondly, I present a detailed and systematic study of the controlled overgrowth of Pd on Au nanorods. The overgrowth of Pd nanoshells with fine-controlled dimensions and architectures on single-crystalline Au nanorods through seed-mediated growth protocol in the presence of various surfactants is investigated. Thirdly, I have demonstrated that creation of high-index facets on subwavelength metallic nanoparticles provides a unique approach to the integration of desired plasmonic and catalytic properties on the same nanoparticle. Through site-selective surface etching of metallic nanocuboids whose surfaces are dominated by low-index facets, I have controllably fabricated nanorice and nanodumbbell particles, which exhibit drastically enhanced catalytic activities arising from the catalytically active high index facets abundant on the particle surfaces. And the nanorice and nanodumbbell particles also possess appealing tunable plasmonic properties that allow us to gain quantitative insights into nanoparticle-catalyzed reactions with unprecedented sensitivity and detail through time

  5. S09 Symposium KK, Structure-Property Relationships in Biomineralized and Biomimetic Composites

    SciTech Connect

    David Kisailus; Lara Estroff; Himadri S. Gupta; William J. Landis; Pablo D. Zavattieri

    2010-06-07

    The technical presentations and discussions at this symposium disseminated and assessed current research and defined future directions in biomaterials research, with a focus on structure-function relationships in biological and biomimetic composites. The invited and contributed talks covered a diverse range of topics from fundamental biology, physics, chemistry, and materials science to potential applications in developing areas such as light-weight composites, multifunctional and smart materials, biomedical engineering, and nanoscaled sensors. The invited speakers were chosen to create a stimulating program with a mixture of established and junior faculty, industrial and academic researchers, and American and international experts in the field. This symposium served as an excellent introduction to the area for younger scientists (graduate students and post-doctoral researchers). Direct interactions between participants also helped to promote potential future collaborations involving multiple disciplines and institutions.

  6. Structure-property relationship in cytotoxicity and cell uptake of poly(2-oxazoline) amphiphiles

    PubMed Central

    Luxenhofer, Robert; Sahay, Gaurav; Schulz, Anita; Alakhova, Daria; Bronich, Tatiana K.; Jordan, Rainer; Kabanov, Alexander V.

    2011-01-01

    The family of poly(2-oxazoline)s (POx) is being increasingly investigated in the context of biomedical applications. We tested the relative cytotoxicity of POx and were able to confirm that these polymers are typically not cytotoxic even at high concentrations. Furthermore, we report structure-uptake relationships of a series of amphiphilic POx block copolymers that have different architectures, molar mass and chain termini. The rate of endocytosis can be fine-tuned over a broad range by changing the polymer structure. The cellular uptake increases with the hydrophobic character of the polymers and is observed even at nanomolar concentrations. Considering the structural versatility of this class of polymers, the relative ease of preparation and their stability underlines the potential of POx as a promising platform candidate for the preparation of next-generation polymer therapeutics. PMID:21513750

  7. Composition-structure-property relationships of commercial polyurethane foams for mattresses

    NASA Astrophysics Data System (ADS)

    Scarfato, P.; Di Maio, L.; D'Arienzo, L.; Rinaldi, S.; Incarnato, L.

    2015-12-01

    Three commercial flexible polyurethane foams used for mattress have been submitted to chemical-physical analyses, water vapor permeability and compression mechanical tests, in order to understand the relationships among their composition, structure, and some functional properties of interest for bedding applications. The results demonstrated that all the three foams have open cell morphology and similar cell structure, with average cell diameters ranging from 430 to 510 micron and wide cell size distribution. As a consequence, they also show comparable water vapor transport behavior. On the contrary, their mechanical response, in terms of hysteresis loss, surface firmness and resistance to bottoming out, was found strongly dependent on their chemical structure and molecular mobility, as inferred from infrared spectroscopy analysis.

  8. Processing-structure-property relationships in electron beam physical vapor deposited yttria stabilized zirconia coatings

    SciTech Connect

    Rao, D. Srinivasa; Valleti, Krishna; Joshi, S. V.; Janardhan, G. Ranga

    2011-05-15

    The physical and mechanical properties of yttria stabilized zirconia (YSZ) coatings deposited by the electron beam physical vapor deposition technique have been investigated by varying the key process variables such as vapor incidence angle and sample rotation speed. The tetragonal zirconia coatings formed under varying process conditions employed were found to have widely different surface and cross-sectional morphologies. The porosity, phase composition, planar orientation, hardness, adhesion, and surface residual stresses in the coated specimens were comprehensively evaluated to develop a correlation with the process variables. Under transverse scratch test conditions, the YSZ coatings exhibited two different crack formation modes, depending on the magnitude of residual stress. The influence of processing conditions on the coating deposition rate, column orientation angle, and adhesion strength has been established. Key relationships between porosity, hardness, and adhesion are also presented.

  9. Relationship between structure, properties, and the radical scavenging activity of morin

    NASA Astrophysics Data System (ADS)

    Mendoza-Wilson, Ana María; Santacruz-Ortega, Hisila; Balandrán-Quintana, René R.

    2011-05-01

    The relationship between structure, kinetic, thermochemical and electronic properties of the morin flavonoid was researched in order to establish the molecular characteristics related to its maximum radical scavenging activity. The reaction of morin with the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH rad ) was carried out in ethanol, through the hydrogen-atom transfer (HAT) mechanism. Morin showed the highest radical scavenging activity under conditions of excess of free radical. It was found, by means of experimental and computational methods, that 3-OH, 2'-OH and 4'-OH are the main reactive sites, as well as that the 3-O-2'-O quinone is the first product of the reaction, tending to prevail in the enol form through a tautomerism effect, whose observed structural arrangement corresponds to the 3-O semiquinone.

  10. Towards the Application of Structure-Property Relationship Modeling in Materials Science: Predicting the Seebeck Coefficient for Ionic Liquid/Redox Couple Systems.

    PubMed

    Sosnowska, Anita; Barycki, Maciej; Gajewicz, Agnieszka; Bobrowski, Maciej; Freza, Sylwia; Skurski, Piotr; Uhl, Stefanie; Laux, Edith; Journot, Tony; Jeandupeux, Laure; Keppner, Herbert; Puzyn, Tomasz

    2016-06-01

    This work focuses on determining the influence of both ionic-liquid (IL) type and redox couple concentration on Seebeck coefficient values of such a system. The quantitative structure-property relationship (QSPR) and read-across techniques are proposed as methods to identify structural features of ILs (mixed with LiI/I2 redox couple), which have the most influence on the Seebeck coefficient (Se ) values of the system. ILs consisting of small, symmetric cations and anions with high values of vertical electron binding energy are recognized as those with the highest values of Se . In addition, the QSPR model enables the values of Se to be predicted for each IL that belongs to the applicability domain of the model. The influence of the redox-couple concentration on values of Se is also quantitatively described. Thus, it is possible to calculate how the value of Se will change with changing redox-couple concentration. The presence of the LiI/I2 redox couple in lower concentrations increases the values of Se , as expected. PMID:26919483

  11. Structure-Property Relationships in Atomic-Scale Junctions: Histograms and Beyond.

    PubMed

    Hybertsen, Mark S; Venkataraman, Latha

    2016-03-15

    Over the past 10 years, there has been tremendous progress in the measurement, modeling and understanding of structure-function relationships in single molecule junctions. Numerous research groups have addressed significant scientific questions, directed both to conductance phenomena at the single molecule level and to the fundamental chemistry that controls junction functionality. Many different functionalities have been demonstrated, including single-molecule diodes, optically and mechanically activated switches, and, significantly, physical phenomena with no classical analogues, such as those based on quantum interference effects. Experimental techniques for reliable and reproducible single molecule junction formation and characterization have led to this progress. In particular, the scanning tunneling microscope based break-junction (STM-BJ) technique has enabled rapid, sequential measurement of large numbers of nanoscale junctions allowing a statistical analysis to readily distinguish reproducible characteristics. Harnessing fundamental link chemistry has provided the necessary chemical control over junction formation, enabling measurements that revealed clear relationships between molecular structure and conductance characteristics. Such link groups (amines, methylsuflides, pyridines, etc.) maintain a stable lone pair configuration that selectively bonds to specific, undercoordinated transition metal atoms available following rupture of a metal point contact in the STM-BJ experiments. This basic chemical principle rationalizes the observation of highly reproducible conductance signatures. Subsequently, the method has been extended to probe a variety of physical phenomena ranging from basic I-V characteristics to more complex properties such as thermopower and electrochemical response. By adapting the technique to a conducting cantilever atomic force microscope (AFM-BJ), simultaneous measurement of the mechanical characteristics of nanoscale junctions as they

  12. Key factors limiting carbon nanotube yarn strength: exploring processing-structure-property relationships.

    PubMed

    Beese, Allison M; Wei, Xiaoding; Sarkar, Sourangsu; Ramachandramoorthy, Rajaprakash; Roenbeck, Michael R; Moravsky, Alexander; Ford, Matthew; Yavari, Fazel; Keane, Denis T; Loutfy, Raouf O; Nguyen, SonBinh T; Espinosa, Horacio D

    2014-11-25

    Studies of carbon nanotube (CNT) based composites have been unable to translate the extraordinary load-bearing capabilities of individual CNTs to macroscale composites such as yarns. A key challenge lies in the lack of understanding of how properties of filaments and interfaces across yarn hierarchical levels govern the properties of macroscale yarns. To provide insight required to enable the development of superior CNT yarns, we investigate the fabrication-structure-mechanical property relationships among CNT yarns prepared by different techniques and employ a Monte Carlo based model to predict upper bounds on their mechanical properties. We study the correlations between different levels of alignment and porosity and yarn strengths up to 2.4 GPa. The uniqueness of this experimentally informed modeling approach is the model's ability to predict when filament rupture or interface sliding dominates yarn failure based on constituent mechanical properties and structural organization observed experimentally. By capturing this transition and predicting the yarn strengths that could be obtained under ideal fabrication conditions, the model provides critical insights to guide future efforts to improve the mechanical performance of CNT yarn systems. This multifaceted study provides a new perspective on CNT yarn design that can serve as a foundation for the development of future composites that effectively exploit the superior mechanical performance of CNTs. PMID:25353651

  13. Structure-property relationships of curved aromatic materials from first principles.

    PubMed

    Zoppi, Laura; Martin-Samos, Layla; Baldridge, Kim K

    2014-11-18

    CONSPECTUS: Considerable effort in the past decade has been extended toward achieving computationally affordable theoretical methods for accurate prediction of the structure and properties of materials. Theoretical predictions of solids began decades ago, but only recently have solid-state quantum techniques become sufficiently reliable to be routinely chosen for investigation of solids as quantum chemistry techniques are for isolated molecules. Of great interest are ab initio predictive theories for solids that can provide atomic scale insights into properties of bulk materials, interfaces, and nanostructures. Adaption of the quantum chemical framework is challenging in that no single theory exists that provides prediction of all observables for every material type. However, through a combination of interdisciplinary efforts, a richly textured and substantive portfolio of methods is developing, which promise quantitative predictions of materials and device properties as well as associated performance analysis. Particularly relevant for device applications are organic semiconductors (OSC), with electrical conductivity between that of insulators and that of metals. Semiconducting small molecules, such as aromatic hydrocarbons, tend to have high polarizabilities, small band-gaps, and delocalized π electrons that support mobile charge carriers. Most importantly, the special nature of optical excitations in the form of a bound electron-hole pairs (excitons) holds significant promise for use in devices, such as organic light emitting diodes (OLEDs), organic photovoltaics (OPVs), and molecular nanojunctions. Added morphological features, such as curvature in aromatic hydrocarbon structure, can further confine the electronic states in one or more directions leading to additional physical phenomena in materials. Such structures offer exploration of a wealth of phenomenology as a function of their environment, particularly due to the ability to tune their electronic

  14. Structure-property relationships of dissimilar friction stir welded aluminum alloys

    NASA Astrophysics Data System (ADS)

    Quinones, Rogie Irwin Rodriguez

    In this work, the relationship between microstructure and mechanical properties of dissimilar friction stir welded AA6061-to-AA7050 aluminum alloys were evaluated. Experimental results from this study revealed that static strength increased with the tool rotational speed and was correlated with the material intermixing. Fully-reversed low cycle fatigue experimental results showed an increase in the strain hardening properties as well as the number of cycles-to-failure as the tool rotational speed was increased. Furthermore, under both static and cyclic loading, fracture of the joint was dominated by the AA6061 alloy side of the weld. In addition, inspection of the fatigue surfaces revealed that cracks initiated from intermetallic particles located near the surface. In order to determine the corrosion resistance of the dissimilar joint, corrosion defects were produced on the crown surface of the weld by static immersion in 3.5% NaCl for various exposure times. Results revealed localized corrosion damage in the thermo-mechanically affected and heat affected zones. Results demonstrated a decrease in the fatigue life, with evidence of crack initiation at the corrosion defects; however, the fatigue life was nearly independent of the exposure time. This can be attributed to total fatigue life dominated by incubation time. Furthermore, two types of failure were observed: fatigue crack initiation in the AA6061 side at high strain amplitudes (>0.3%); and fatigue crack initiation in the AA7050 side at low strain amplitudes (<0.2%). Lastly, a microstructure-sensitive model based on a multi-stage fatigue damage concept was extended to the dissimilar friction stir welded joints in order to capture the crack initiation and propagation in as-welded and pre-corroded conditions. Good correlation between experimental fatigue results and the model was achieved based on the variation in the initial defect size, microstructure, and mechanical properties of the dissimilar friction stir

  15. Structure-Property Relationships in Lithium, Silver, and Cesium Uranyl Borates

    SciTech Connect

    Wang, Shuao; Alekseev, Evgeny V.; Stritzinger, Jared T.; Liu, Guokui; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.

    2010-11-09

    Four new uranyl borates, Li[UO{sub 2}B{sub 5}O{sub 9}]·H{sub 2}O (LiUBO-1), Ag[(UO{sub 2})B{sub 5}O{sub 8}(OH){sub 2}] (AgUBO-1), α-Cs[(UO{sub 2}){sub 2}B{sub 11}O{sub 16}(OH){sub 6}] (CsUBO-1), and β-Cs[(UO{sub 2}){sub 2}B{sub 11}O{sub 16}(OH){sub 6}] (CsUBO-2) were synthesized via the reaction of uranyl nitrate with a large excess of molten boric acid in the presence of lithium, silver, or cesium nitrate. These compounds share a common structural motif consisting of a linear uranyl, UO{sub 2}{sup 2+}, cation surrounded by BO{sub 3} triangles and BO{sub 4} tetrahedra to create an UO{sub 8} hexagonal bipyramidal environment around uranium. The borate anions bridge between uranyl units to create sheets. Additional BO{sub 3} triangles extend from the polyborate layers, and are directed approximately perpendicular to the sheets. In Li[(UO{sub 2})B{sub 5}O{sub 9}]·H{sub 2}O, the additional BO{sub 3} triangles connect these sheets together to form a three-dimensional framework structure. Li[UO{sub 2})B{sub 5}O{sub 9}]·H{sub 2}O and β-Cs[(UO{sub 2}){sub 2}B{sub 11}O{sub 16}(OH){sub 6}] adopt noncentrosymmetric structures, while Ag[(UO{sub 2})B{sub 5}O{sub 8}(OH){sub 2}] and α-Cs[(UO{sub 2}){sub 2}B{sub 11}O{sub 16}(OH){sub 6}] are centrosymmetric. Li[(UO{sub 2})B{sub 5}O{sub 9}]·H{sub 2}O, which can be obtained as pure phase, displays second-harmonic generation of 532 nm light from 1064 nm light. Topological relationships of all actinyl borates are developed.

  16. Structure-Property Relationships in Polymer Derived Amorphous/Nano-Crystalline Silicon Carbide for Nuclear Applications

    SciTech Connect

    Zunjarrao, Suraj C.; Singh, Abhishek K.; Singh, Raman P.

    2006-07-01

    difficulties in interpreting 'true' properties from bulk measurements. Hence, hardness and modulus measurements are carried out using instrumented nano-indentation to establish property--structure relationship for SiC derived from the polymer precursor. It is seen that the presence of nanocrystalline domains in amorphous SiC significantly influences the modulus and hardness. (authors)

  17. Structure-property relationships in novel polymers and block copolymers from ring-opening metathesis polymerization

    NASA Astrophysics Data System (ADS)

    Bishop, John Paul

    2011-12-01

    crystallites, limiting their lateral growth and generating composite hard domains with both crystalline and glassy components. The pentablocks show the low initial modulus, strain-hardening behavior, and small permanent set desired for TPEs, while retaining an easily-processed single-phase melt. We found that the chain microstructure (cis/trans ratio) in the ROMP of norbornene and methyltetracyclododecene (MTD) using a so-called Schrock-type initiator to be a strong function of monomer concentration, providing a convenient means for tuning the average trans content in the resulting polymers. The results are explained based on a literature kinetic description for the behavior of this initiator, which allowed for the development of a quantitative model to describe the observed experimental data. In contrast, ROMP of MTD using the first-generation Grubbs initiator showed no dependence of the trans content on monomer concentration. hPN is unusual in that it is highly crystalline despite having an atactic placement of its backbone cyclopentylene rings. Furthermore, it has a crystal-crystal transition at elevated temperatures (˜110°C) where the crystal structure transforms from a conventional, three-dimensionally-ordered monoclinic lattice at lower temperatures to a high-temperature crystal polymorph that is rotationally disordered and shows a pseudo-hexagonal packing transverse to the chain axes. The tacticity of hPN, measured to first order as the ratio of meso to racemo dyads (m:r), was varied by altering the synthesis conditions, and was shown to have a direct correlation with the temperature at which the crystal-crystal transition occurs (T cc). Small changes in m:r (from 0.8 to 1.1) are sufficient to raise Tcc by nearly 20°C. When heated above Tcc, hPN crystals thicken at a rate much greater than conventional three-dimensionally-ordered crystals, but below the rates shown by the two-dimensional hexagonal (columnar) phase formed by some polymers. Finally, we report the

  18. A quantitative structure-property relationship (QSPR) study of singlet oxygen generation by pteridines.

    PubMed

    Buglak, Andrey A; Telegina, Taisiya A; Kritsky, Mikhail S

    2016-06-01

    The QSPR method is used in photochemistry for the prediction of the absorption wavelength, fluorescence intensity, photolysis quantum yield, etc. However, to our knowledge, no attempts have been made to use the quantum yield of singlet oxygen ((1)O2) generation (ΦΔ) as an analyzed parameter in a QSPR study. We performed QSPR analysis of 29 pteridine compounds (including pterin and flavin sensitizers) for their ability to produce singlet oxygen in aqueous (D2O) solutions. Pteridines are ubiquitously present in living systems (mostly as coenzymes), possess high photochemical activity and have multiple applications as photosensitizers. Our goal was to develop a QSPR model for the fast virtual screening and prediction of the (1)O2 generation quantum yield of pteridines. Quantum-chemical descriptors were calculated using the AM1 semi-empirical method. The ability of pteridines to generate singlet oxygen was found to be significantly correlated with the HOMO orbital energy (R(2) = 0.806) and electronegativity (R(2) = 0.840). The best QSPR model obtained using electronegativity, dipole density and electrostatic charge of the N3 atom of the pteridine system allows us to predict ΦΔ of pterin and flavin photosensitizers. The model possesses high internal stability (q(2) = 0.881), as well as high predicting ability for the external dataset (pred_R(2) = 0.873). More QSPR analysis is needed for the prediction of ΦΔ of pteridines and other groups of sensitizers in aqueous as well as in non-polar solutions. PMID:27216311

  19. Quantitative structure-property relationships for chemical functional use and weight fractions in consumer articles

    EPA Science Inventory

    Chemical functional use -- the functional role a chemical plays in processes or products -- may be a useful heuristic for predicting human exposure potential in that it comprises information about the compound's likely physical properties and the product formulations or articles ...

  20. Electron Backscatter Diffraction: An Important Tool for Analyses of Structure-Property Relationships in Thin-Film Solar Cells

    NASA Astrophysics Data System (ADS)

    Abou-Ras, D.; Kavalakkatt, J.; Nichterwitz, M.; Schäfer, N.; Harndt, S.; Wilkinson, A. J.; Tsyrulin, K.; Schulz, H.; Bauer, F.

    2013-09-01

    The present work gives an overview of the application of electron backscatter diffraction (EBSD) in the field of thin-film solar cells, which consist of stacks of polycrystalline layers on various rigid or flexible substrates. EBSD provides access to grain-size and local-orientation distributions, film textures, and grain-boundary types. By evaluation of the EBSD patterns within individual grains of the polycrystalline solar cell layers, microstrain distributions also can be obtained. These microstructural properties are of considerable interest for research and development of thin-film solar cells. Moreover, EBSD may be performed three-dimensionally, by alternating slicing of cross sections in a focused ion-beam machine and EBSD acquisition. To relate the microstructural properties to the electrical properties of individual layers as well as to the device performances of corresponding solar cells, EBSD can be combined with electron-beam-induced current and cathodoluminescence measurements and with various scanning-probe microscopy methods such as Kelvin-probe force, scanning spreading resistance, or scanning capacitance microscopy on identical specimen positions. Together with standard device characterization of thin-film solar cells, these scanning microscopy measurements provide the means for extensive analysis of structure-property relationships in solar-cell stacks with polycrystalline layers.

  1. Supramolecular Dimerization and [2 + 2] Photocycloaddition Reactions of Crown Ether Styryl Dyes Containing a Tethered Ammonium Group: Structure-Property Relationships.

    PubMed

    Ushakov, Evgeny N; Vedernikov, Artem I; Lobova, Natalia A; Dmitrieva, Svetlana N; Kuz'mina, Lyudmila G; Moiseeva, Anna A; Howard, Judith A K; Alfimov, Michael V; Gromov, Sergey P

    2015-12-31

    Molecular self-assembly is an effective strategy for controlling the [2 + 2] photocycloaddition reaction of olefins. The geometrical properties of supramolecular assemblies are proven to have a critical effect on the efficiency and selectivity of this photoreaction both in the solid state and in solution, but the role of other factors remains poorly understood. Convenient supramolecular systems to study the structure-property relationships are pseudocyclic dimers spontaneously formed by styryl dyes containing a crown ether moiety and a remote ammonium group. New dyes of this type were synthesized to investigate the effects of structural and electronic factors on the quantitative characteristics of supramolecular dimerization and [2 + 2] photocycloaddition in solution. Variable structural parameters for the styryl dyes were the size and structure of macrocyclic moiety, the nature of heteroaromatic residue, and the length of the ammonioalkyl group attached to this residue. Quantum chemical calculations of the pseudocyclic dimers were performed in order to interpret the relationships between the structure of the ammonium dyes and the efficiency of the supramolecular photoreaction. One of the dimeric complexes was obtained in the crystalline state and studied by X-ray diffraction. The results obtained demonstrate that the photocycloaddition in the pseudocyclic dimers can be dramatically affected by the electronic structure of the styryl moieties, as dependent on the electron-donating ability of the substituents on the benzene ring, and by the conformational flexibility of the pseudocycle, which determines the mobility of the olefinic bonds. The significance of electronic factors is highlighted by the fact that the photocycloaddition quantum yield in geometrically similar dimeric structures varies from ≤10(-4) to 0.38. The latter value is unusually high for olefins in solution. PMID:26650887

  2. Polymer Physics and Structure/property Relationships of Thermally Stable Polyarylene Ethers for Second Order Nonlinear Optics.

    NASA Astrophysics Data System (ADS)

    Fu, Chu-Yun Stacey

    1995-01-01

    Over the past decade, researchers have been actively involved in developing nonlinear optical polymers for device applications. One major obstacle with the current polymers is that the chromophores doped or covalently bonded to the backbones disorient following electric field poling and thus the nonlinear optical signal decreases with time. The optical stability must thus be optimized before useful devices made from these materials will be feasible. Although several synthetic approaches have been employed to optimize polymer structures and glass transition temperatures in order to maximize stability, the studies of the polymer physics of these high temperature stable polymers are still limited. It is critical to understand the polymer physics governing the relaxation behavior of these nonlinear optical polymers so that one can better predict the long-term thermal and temporal stability and changes in properties throughout the anticipated service life when utilizing them for device applications. The goal of this research is to investigate the structure/property relationships that influence the relaxation behavior of a class of thermally stable polymers called polyarylene ethers (synthesized by Dr. Duane B. Priddy, Jr., Mr. Greg D. Lyle, and Dr. James E. McGrath at Virginia Polytechnic Institute and State University). Specific issues such as the effects of polymer backbone structures, dopant/polymer interactions, chromophore functionalization, and chromophore concentration on the dopant orientational dynamics and intermolecular cooperativity in these polymer systems were studied. Attempts to correlate the molecular level parameters including the molecular weight and polydispersities to the observed physical properties were made. The effect of physical aging during poling on the chromophore orientational dynamics was also examined. Second harmonic generation, a second order nonlinear optical effect, and dielectric relaxation are the two techniques employed for these

  3. A novel approach to study the structure-property relationships and applications in living systems of modular Cu2+ fluorescent probes

    NASA Astrophysics Data System (ADS)

    She, Mengyao; Yang, Zheng; Hao, Likai; Wang, Zhaohui; Luo, Tianyou; Obst, Martin; Liu, Ping; Shen, Yehua; Zhang, Shengyong; Li, Jianli

    2016-08-01

    A series of Cu2+ probe which contains 9 probes have been synthesized and established. All the probes were synthesized using Rhodamine B as the fluorophore, conjugated to various differently substituted cinnamyl aldehyde with C=N Schiff base structural motif as their core moiety. The structure-property relationships of these probes have been investigated. The change of optical properties, caused by different electronic effect and steric effect of the recognition group, has been analyzed systematically. DFT calculation simulation of the Ring-Close and Ring-Open form of all the probes have been employed to illuminate, summarize and confirm these correlations between optical properties and molecular structures. In addition, biological experiment demonstrated that all the probes have a high potential for both sensitive and selective detection, mapping of adsorbed Cu2+ both in vivo and environmental microbial systems. This approach provides a significant strategy for studying structure-property relationships and guiding the synthesis of probes with various optical properties.

  4. Synthesis, growth, vibrational spectral investigations and structure-property relationship of an organic NLO crystal: 3,4-Dimethoxy chalcone

    NASA Astrophysics Data System (ADS)

    Alen, S.; Sajan, D.; Joseph, Lynnette; Chaitanya, K.; Shettigar, Venkataraya; Jothy, V. Bena

    2015-09-01

    3,4-Dimethoxy chalcone, a nonlinear optical material, was synthesized and noncentro symmetric single crystals were grown in solution by slow evaporation technique. Thermal analysis such as DSC revealed a good thermal stability of 3,4-dimethoxy chalcone. The FT-IR and FT-Raman spectral studies were carried out to investigate the structural properties of the title compound. The molecular orbitals and natural bond analysis of this material were calculated by Density Functional Theory calculations. The second harmonic conversion efficiency was determined using the Kurtz powder technique, which is 8 times that of urea.

  5. A novel approach to study the structure-property relationships and applications in living systems of modular Cu(2+) fluorescent probes.

    PubMed

    She, Mengyao; Yang, Zheng; Hao, Likai; Wang, Zhaohui; Luo, Tianyou; Obst, Martin; Liu, Ping; Shen, Yehua; Zhang, Shengyong; Li, Jianli

    2016-01-01

    A series of Cu(2+) probe which contains 9 probes have been synthesized and established. All the probes were synthesized using Rhodamine B as the fluorophore, conjugated to various differently substituted cinnamyl aldehyde with C=N Schiff base structural motif as their core moiety. The structure-property relationships of these probes have been investigated. The change of optical properties, caused by different electronic effect and steric effect of the recognition group, has been analyzed systematically. DFT calculation simulation of the Ring-Close and Ring-Open form of all the probes have been employed to illuminate, summarize and confirm these correlations between optical properties and molecular structures. In addition, biological experiment demonstrated that all the probes have a high potential for both sensitive and selective detection, mapping of adsorbed Cu(2+) both in vivo and environmental microbial systems. This approach provides a significant strategy for studying structure-property relationships and guiding the synthesis of probes with various optical properties. PMID:27485974

  6. A novel approach to study the structure-property relationships and applications in living systems of modular Cu2+ fluorescent probes

    PubMed Central

    She, Mengyao; Yang, Zheng; Hao, Likai; Wang, Zhaohui; Luo, Tianyou; Obst, Martin; Liu, Ping; Shen, Yehua; Zhang, Shengyong; Li, Jianli

    2016-01-01

    A series of Cu2+ probe which contains 9 probes have been synthesized and established. All the probes were synthesized using Rhodamine B as the fluorophore, conjugated to various differently substituted cinnamyl aldehyde with C=N Schiff base structural motif as their core moiety. The structure-property relationships of these probes have been investigated. The change of optical properties, caused by different electronic effect and steric effect of the recognition group, has been analyzed systematically. DFT calculation simulation of the Ring-Close and Ring-Open form of all the probes have been employed to illuminate, summarize and confirm these correlations between optical properties and molecular structures. In addition, biological experiment demonstrated that all the probes have a high potential for both sensitive and selective detection, mapping of adsorbed Cu2+ both in vivo and environmental microbial systems. This approach provides a significant strategy for studying structure-property relationships and guiding the synthesis of probes with various optical properties. PMID:27485974

  7. Structure-Property-Performance Relationships for Organic Photovoltaics and the Utilization of Photoconducting Atomic Force Microscopy for Characterizing Organic Thin Films

    NASA Astrophysics Data System (ADS)

    Guide, Michele Elyse

    Progress in the development of organic photovoltaics (OPVs) depends on a continually growing understanding of the effects of chemical composition or processing method on the optoelectronic and structural properties and, in turn, how those properties influence device performance. Unfortunately, no single characterization method can provide all of the necessary information to develop these structure-property-performance relationships. This thesis details examples of structure-property-performance studies in which multiple characterization methods are used to identify the root cause of limited device performance for a particular photovoltaic system. As a large part of this work, the refinement and utilization of a nanoscale characterization technique, namely photoconducting atomic force microscopy (pc-AFM) is presented, not as an alternative to other characterization methods, but as a unique approach to characterizing the nanoscale morphology and local optoelectronic properties of an organic thin film simultaneously. The goal of this work was to make pc-AFM as robust and reliable a characterization tool and as close an analog to bulk OPV performance testing as possible. The first sections of this thesis focus on the development of pc-AFM for the characterization of OPVs. The capabilities of pc-AFM at the time this research commenced are illustrated in a study of a multilayered p/i/n architecture OPV system comprising a thermoset small molecule donor, tetrabenzoporphyrin (BP) and one of two structurally similar soluble fullerene derivative acceptors. By investigating the nanoscale topography, dark current, and photocurrent in each layer of these multilayer devices, the differences in bulk device performance can be rationalized and the composition of specific morphological features can be identified. At the same time, this study demonstrates how interpretation of pc-AFM measurements was not straightforward and required knowledge of the bulk performance. This issue

  8. Predictivity Approach for Quantitative Structure-Property Models. Application for Blood-Brain Barrier Permeation of Diverse Drug-Like Compounds

    PubMed Central

    Bolboacă, Sorana D.; Jäntschi, Lorentz

    2011-01-01

    The goal of the present research was to present a predictivity statistical approach applied on structure-based prediction models. The approach was applied to the domain of blood-brain barrier (BBB) permeation of diverse drug-like compounds. For this purpose, 15 statistical parameters and associated 95% confidence intervals computed on a 2 × 2 contingency table were defined as measures of predictivity for binary quantitative structure-property models. The predictivity approach was applied on a set of compounds comprised of 437 diverse molecules, 122 with measured BBB permeability and 315 classified as active or inactive. A training set of 81 compounds (~2/3 of 122 compounds assigned randomly) was used to identify the model and a test set of 41 compounds was used as the internal validation set. The molecular descriptor family on vertices cutting was the computation tool used to generate and calculate structural descriptors for all compounds. The identified model was assessed using the predictivity approach and compared to one model previously reported. The best-identified classification model proved to have an accuracy of 69% in the training set (95%CI [58.53–78.37]) and of 73% in the test set (95%CI [58.32–84.77]). The predictive accuracy obtained on the external set proved to be of 73% (95%CI [67.58–77.39]). The classification model proved to have better abilities in the classification of inactive compounds (specificity of ~74% [59.20–85.15]) compared to abilities in the classification of active compounds (sensitivity of ~64% [48.47–77.70]) in the training and external sets. The overall accuracy of the previously reported model seems not to be statistically significantly better compared to the identified model (~81% [71.45–87.80] in the training set, ~93% [78.12–98.17] in the test set and ~79% [70.19–86.58] in the external set). In conclusion, our predictivity approach allowed us to characterize the model obtained on the investigated set of

  9. Chemical Modification of Graphene Oxide through Diazonium Chemistry and Its Influence on the Structure-Property Relationships of Graphene Oxide-Iron Oxide Nanocomposites.

    PubMed

    Rebuttini, Valentina; Fazio, Enza; Santangelo, Saveria; Neri, Fortunato; Caputo, Gianvito; Martin, Cédric; Brousse, Thierry; Favier, Frédéric; Pinna, Nicola

    2015-08-24

    4-Carboxyphenyl groups are covalently grafted onto graphene oxide via diazonium chemistry for studying their role on the adsorption of iron oxide nanoparticles. The nanoparticles are deposited via a novel phase-transfer approach involving specific interactions at the interface between two immiscible solvents. The increased density and the homogeneous distribution of surface carboxyl moieties enable the preparation of a nanocomposite with improved iron oxide distribution and loading. Structure-properties relationships are investigated by analysing the electrochemical properties of the nanocomposites, which are regarded as promising active materials for application in supercapacitors. It is demonstrated that the nature of the interactions between the components similarly affects the overall electrochemical performances of the nanocomposites and the structure of the materials. PMID:26178747

  10. Revealing the structure-property relationship of covalent organic frameworks for CO₂ capture from postcombustion gas: a multi-scale computational study.

    PubMed

    Tong, Minman; Yang, Qingyuan; Xiao, Yuanlong; Zhong, Chongli

    2014-08-01

    With the aid of multi-scale computational methods, a diverse set of 46 covalent organic frameworks (COFs), covering the most typical COFs synthesized to date, were collected to study the structure-property relationship of COFs for CO2 capture. For this purpose, CO2 capture from postcombustion gas (CO2-N2 mixture) under industrial vacuum swing adsorption (VSA) conditions was considered as an example. This work shows that adsorption selectivity, CO2 working capacity and the sorbent selection parameter of COFs all exhibit strong correlation with the difference in the adsorbility of adsorbates (ΔAD), highlighting that realization of large ΔAD can be regarded as an important starting point for designing COFs with improved separation performance. Furthermore, it was revealed that the separation performance of 2D-layered COFs can be greatly enhanced by generating "splint effects", which can be achieved through structural realignment to form slit-like pores with suitable size in the structures. Such "splint effects" in 2D-COFs can find their similar counterpart of "catenation effects" in 3D-COFs or MOFs. On the basis of these observations, a new design strategy was proposed to strengthen the separation performance of COFs. It could be expected that the information obtained in this work not only will enrich the knowledge of the structure-property relationship of COFs for separation, but also will largely facilitate their future applications to the fields related to energy and environmental science, such as natural gas purification, CO2, NO(x) and SO(x) capture, etc. PMID:24936781

  11. Probing Carrier Transport and Structure-Property Relationship of Highly Ordered Organic Semiconductors at the Two-Dimensional Limit.

    PubMed

    Zhang, Yuhan; Qiao, Jingsi; Gao, Si; Hu, Fengrui; He, Daowei; Wu, Bing; Yang, Ziyi; Xu, Bingchen; Li, Yun; Shi, Yi; Ji, Wei; Wang, Peng; Wang, Xiaoyong; Xiao, Min; Xu, Hangxun; Xu, Jian-Bin; Wang, Xinran

    2016-01-01

    One of the basic assumptions in organic field-effect transistors, the most fundamental device unit in organic electronics, is that charge transport occurs two dimensionally in the first few molecular layers near the dielectric interface. Although the mobility of bulk organic semiconductors has increased dramatically, direct probing of intrinsic charge transport in the two-dimensional limit has not been possible due to excessive disorders and traps in ultrathin organic thin films. Here, highly ordered single-crystalline mono- to tetralayer pentacene crystals are realized by van der Waals (vdW) epitaxy on hexagonal BN. We find that the charge transport is dominated by hopping in the first conductive layer, but transforms to bandlike in subsequent layers. Such an abrupt phase transition is attributed to strong modulation of the molecular packing by interfacial vdW interactions, as corroborated by quantitative structural characterization and density functional theory calculations. The structural modulation becomes negligible beyond the second conductive layer, leading to a mobility saturation thickness of only ∼3  nm. Highly ordered organic ultrathin films provide a platform for new physics and device structures (such as heterostructures and quantum wells) that are not possible in conventional bulk crystals. PMID:26799035

  12. Probing Carrier Transport and Structure-Property Relationship of Highly Ordered Organic Semiconductors at the Two-Dimensional Limit

    NASA Astrophysics Data System (ADS)

    Zhang, Yuhan; Qiao, Jingsi; Gao, Si; Hu, Fengrui; He, Daowei; Wu, Bing; Yang, Ziyi; Xu, Bingchen; Li, Yun; Shi, Yi; Ji, Wei; Wang, Peng; Wang, Xiaoyong; Xiao, Min; Xu, Hangxun; Xu, Jian-Bin; Wang, Xinran

    2016-01-01

    One of the basic assumptions in organic field-effect transistors, the most fundamental device unit in organic electronics, is that charge transport occurs two dimensionally in the first few molecular layers near the dielectric interface. Although the mobility of bulk organic semiconductors has increased dramatically, direct probing of intrinsic charge transport in the two-dimensional limit has not been possible due to excessive disorders and traps in ultrathin organic thin films. Here, highly ordered single-crystalline mono- to tetralayer pentacene crystals are realized by van der Waals (vdW) epitaxy on hexagonal BN. We find that the charge transport is dominated by hopping in the first conductive layer, but transforms to bandlike in subsequent layers. Such an abrupt phase transition is attributed to strong modulation of the molecular packing by interfacial vdW interactions, as corroborated by quantitative structural characterization and density functional theory calculations. The structural modulation becomes negligible beyond the second conductive layer, leading to a mobility saturation thickness of only ˜3 nm . Highly ordered organic ultrathin films provide a platform for new physics and device structures (such as heterostructures and quantum wells) that are not possible in conventional bulk crystals.

  13. Quantitative structure-activity relationships for fluoroelastomer/chlorofluorocarbon systems

    SciTech Connect

    Paciorek, K.J.L.; Masuda, S.R.; Nakahara, J.H. ); Snyder, C.E. Jr.; Warner, W.M. )

    1991-12-01

    This paper reports on swell, tensile, and modulus data that were determined for a fluoroelastomer after exposure to a series of chlorofluorocarbon model fluids. Quantitative structure-activity relationships (QSAR) were developed for the swell as a function of the number of carbons and chlorines and for tensile strength as a function of carbon number and chlorine positions in the chlorofluorocarbons.

  14. Parallel high-throughput screening of polymer vectors for nonviral gene delivery: evaluation of structure-property relationships of transfection.

    PubMed

    Rinkenauer, Alexandra C; Vollrath, Antje; Schallon, Anja; Tauhardt, Lutz; Kempe, Kristian; Schubert, Stephanie; Fischer, Dagmar; Schubert, Ulrich S

    2013-09-01

    In recent years, "high-throughput" (HT) has turned into a keyword in polymer research. In this study, we present a novel HT workflow for the investigation of cationic polymers for gene delivery applications. For this purpose, various poly(ethylene imine)s (PEI) were used as representative vectors and investigated via HT-assays in a 96-well plate format, starting from polyplex preparation up to the examination of the transfection process. In detail, automated polyplex preparation, complex size determination, DNA binding affinity, polyplex stability, cytotoxicity, and transfection efficiency were performed in the well plate format. With standard techniques, investigation of the biological properties of polymers is quite time-consuming, so only a limited number of materials and conditions (such as pH, buffer composition, and concentration) can be examined. The approach described here allows many different polymers and parameters to be tested for transfection properties and cytotoxicity, giving faster insights into structure-activity relationships for biological activity. PMID:23886244

  15. Friction stir welding of thin-sheet, age-hardenable aluminum alloys: A study of process/structure/property relationships

    NASA Astrophysics Data System (ADS)

    Shukla, Alpesh Khushalchand

    Friction Stir Welding (FSW) is a relatively new joining process that, as a solid-state process, offers several advantages over conventional fusion welding. Although FSW has been used extensively for the joining of age-hardenable aluminum alloys, the detailed effects of process parameters on the microstructures and mechanical properties of these welds have not been studied, especially for thin-sheet alloys. The present study investigated the FSW of thin-sheet, age-hardenable aluminum alloys, including: the development and optimization of welding process parameters that produce high-integrity, defect-free welds; the systematic evaluation of the effect of the base metal microstructure, FSW process parameters, and corresponding weld zone thermal conditions on microstructure evolution across the weld zone; the analysis of FSW mechanical properties and fracture behavior; and the development of relationships between the process parameters, microstructure, properties, and fracture that allow the optimization of weld performance. Two alloy systems, viz., Al-Cu-Mg (2024) and Al-Cu-Li (2195) in naturally-aged and artificially-aged conditions, respectively, were studied. Process optimization in 1 mm thick 2024-T3 sheet resulted in superior properties versus those of FS welds in thick sheet and plate, and nearly 100% joint efficiency. Microstructures, hardness and tensile properties of FS welds in 2024-T3 exhibited a strong dependency on process parameters. The heat of welding promoted various weld zone microstructures that were produced via the dissolution of base metal GPB zones, the nucleation of GBP and GPB II, and the nucleation and coarsening of S phase. SZ hardness for 2024-T3 welds exhibited a strong, but unusual dependency on the FSW process parameters, which was related to different mechanisms related to GPB zone formation. The microstructures of FS welds in 1 mm thick 2195-T8 were generally insensitive to the FSW process parameters. For all weld heat inputs, FSW

  16. Partitioning and lipophilicity in quantitative structure-activity relationships.

    PubMed Central

    Dearden, J C

    1985-01-01

    The history of the relationship of biological activity to partition coefficient and related properties is briefly reviewed. The dominance of partition coefficient in quantitation of structure-activity relationships is emphasized, although the importance of other factors is also demonstrated. Various mathematical models of in vivo transport and binding are discussed; most of these involve partitioning as the primary mechanism of transport. The models describe observed quantitative structure-activity relationships (QSARs) well on the whole, confirming that partitioning is of key importance in in vivo behavior of a xenobiotic. The partition coefficient is shown to correlate with numerous other parameters representing bulk, such as molecular weight, volume and surface area, parachor and calculated indices such as molecular connectivity; this is especially so for apolar molecules, because for polar molecules lipophilicity factors into both bulk and polar or hydrogen bonding components. The relationship of partition coefficient to chromatographic parameters is discussed, and it is shown that such parameters, which are often readily obtainable experimentally, can successfully supplant partition coefficient in QSARs. The relationship of aqueous solubility with partition coefficient is examined in detail. Correlations are observed, even with solid compounds, and these can be used to predict solubility. The additive/constitutive nature of partition coefficient is discussed extensively, as are the available schemes for the calculation of partition coefficient. Finally the use of partition coefficient to provide structural information is considered. It is shown that partition coefficient can be a valuable structural tool, especially if the enthalpy and entropy of partitioning are available. PMID:3905374

  17. Learning Quantitative Sequence-Function Relationships from Massively Parallel Experiments

    NASA Astrophysics Data System (ADS)

    Atwal, Gurinder S.; Kinney, Justin B.

    2016-03-01

    A fundamental aspect of biological information processing is the ubiquity of sequence-function relationships—functions that map the sequence of DNA, RNA, or protein to a biochemically relevant activity. Most sequence-function relationships in biology are quantitative, but only recently have experimental techniques for effectively measuring these relationships been developed. The advent of such "massively parallel" experiments presents an exciting opportunity for the concepts and methods of statistical physics to inform the study of biological systems. After reviewing these recent experimental advances, we focus on the problem of how to infer parametric models of sequence-function relationships from the data produced by these experiments. Specifically, we retrace and extend recent theoretical work showing that inference based on mutual information, not the standard likelihood-based approach, is often necessary for accurately learning the parameters of these models. Closely connected with this result is the emergence of "diffeomorphic modes"—directions in parameter space that are far less constrained by data than likelihood-based inference would suggest. Analogous to Goldstone modes in physics, diffeomorphic modes arise from an arbitrarily broken symmetry of the inference problem. An analytically tractable model of a massively parallel experiment is then described, providing an explicit demonstration of these fundamental aspects of statistical inference. This paper concludes with an outlook on the theoretical and computational challenges currently facing studies of quantitative sequence-function relationships.

  18. Ultrafast optical nonlinearities and figures of merit in acceptor-substituted 3,4,5-trimethoxy chalcone derivatives: Structure-property relationships

    NASA Astrophysics Data System (ADS)

    Gu, Bing; Ji, Wei; Patil, P. S.; Dharmaprakash, S. M.

    2008-05-01

    By performing both Z-scan and transient transmission measurements with 130 fs laser pulses in the near infrared region, we investigated structure-property relationships for χ(3) in acceptor-substituted 3,4,5-trimethoxy chalcone derivatives. We determined all nonlinear parameters, including two-photon absorption (2PA) cross section, 2PA-induced excited-state absorption (ESA) cross section, microscopic second-order hyperpolarizability, and lifetime of the excited state in these molecules. We found that the microscopic second-order hyperpolarizability γR and 2PA cross section σ2PA in chalcone derivatives increase as the acceptor strength of the molecules increases, which demonstrates an enhancement in optical nonlinearities by simple structural variations. We evaluated the one-photon, two-photon, and effective three-photon figures of merit for acetone solutions of chalcone derivatives at irradiance of 100 GW/cm2. Furthermore, we observed optical limiting behavior in these compounds, which result from both 2PA and 2PA-assisted ESA. These results indicated that chalcone derivatives are a promising candidate for applications on nonlinear photonic devices.

  19. Structure-property relationships in an Al matrix Ca nanofilamentary composite conductor with potential application in high-voltage power transmission

    NASA Astrophysics Data System (ADS)

    Tian, Liang

    This study investigated the processing-structure-properties relationships in an Al/Ca composites using both experiments and modeling/simulation. A particular focus of the project was understanding how the strength and electrical conductivity of the composite are related to its microstructure in the hope that a conducting material with light weight, high strength, and high electrical conductivity can be developed to produce overhead high-voltage power transmission cables. The current power transmission cables (e.g., Aluminum Conductor Steel Reinforced (ACSR)) have acceptable performance for high-voltage AC transmission, but are less well suited for high-voltage DC transmission due to the poorly conducting core materials that support the cable weight. This Al/Ca composite was produced by powder metallurgy and severe plastic deformation by extrusion and swaging. The fine Ca metal powders have been produced by centrifugal atomization with rotating liquid oil quench bath, and a detailed study about the atomization process and powder characteristics has been conducted. The microstructure of Al/Ca composite was characterized by electron microscopy. Microstructure changes at elevated temperature were characterized by thermal analysis and indirect resistivity tests. The strength and electrical conductivity were measured by tensile tests and four-point probe resistivity tests. Predicting the strength and electrical conductivity of the composite was done by micro-mechanics-based analytical modeling. Microstructure evolution was studied by mesoscale-thermodynamics-based phase field modeling and a preliminary atomistic molecular dynamics simulation. The application prospects of this composite was studied by an economic analysis. This study suggests that the Al/Ca (20 vol. %) composite shows promise for use as overhead power transmission cables. Further studies are needed to measure the corrosion resistance, fatigue properties and energized field performance of this composite.

  20. Quantitative Structure – Property Relationship Modeling of Remote Liposome Loading Of Drugs

    PubMed Central

    Cern, Ahuva; Golbraikh, Alexander; Sedykh, Aleck; Tropsha, Alexander; Barenholz, Yechezkel; Goldblum, Amiram

    2012-01-01

    Remote loading of liposomes by trans-membrane gradients is used to achieve therapeutically efficacious intra-liposome concentrations of drugs. We have developed Quantitative Structure Property Relationship (QSPR) models of remote liposome loading for a dataset including 60 drugs studied in 366 loading experiments internally or elsewhere. Both experimental conditions and computed chemical descriptors were employed as independent variables to predict the initial drug/lipid ratio (D/L) required to achieve high loading efficiency. Both binary (to distinguish high vs. low initial D/L) and continuous (to predict real D/L values) models were generated using advanced machine learning approaches and five-fold external validation. The external prediction accuracy for binary models was as high as 91–96%; for continuous models the mean coefficient R2 for regression between predicted versus observed values was 0.76–0.79. We conclude that QSPR models can be used to identify candidate drugs expected to have high remote loading capacity while simultaneously optimizing the design of formulation experiments. PMID:22154932

  1. The synthesis, characterization, and structure-property relationships of regioregular 4,4'-dialkyl-2,2'-bithiazole oligomers and polymers

    NASA Astrophysics Data System (ADS)

    Nanos, John I.

    2005-12-01

    The 4,4'-dialkyl-2,2'-bithiazole moiety can be efficiently coupled to produce well-defined oligomers or block co-oligomers via Stille reactions of mono-bromo and tin substituted precursors. Dehalogenative polycondensations produce high molecular weight homo-polymers and Stille coupling of dibromo and di-tin monomers yields alternating copolymers. The symmetry of the bithiazole monomeric unit produces regioregular oligomers and polymers with the HH-TT dyad sequence. Model compound oligomers were synthesized and studied to explore the progression of structure property relationships with main chain extension. DSC measurements indicate the potential presence of at least three phases in solution cast thin films---the disordered isotropic melt, a stable low temperature morphology designated the alpha-phase, and a high temperature meta-stable morphology designated the beta-phase. Melt transition temperatures are inversely proportional to side alkyl chain length and directly proportional to main chain length and the interplay between the two effects greatly influences the observed thermochromism. Temperature dependent IR studies show an increase in the gauche conformations of the side chains at the low temperature alpha-beta phase transition and main chain twisting at the beta-isotropic transition. The onset of side chain and main chain motion at these phase transition temperatures was confirmed with variable temperature solid state NMR. Temperature dependent XRD results indicate the presence of a solid-to-solid crystal phase change at the low temperature transition followed by formation of preferred orientations of the beta and alpha ordered phases upon cooling from the isotropic melt. The solid-to-solid crystal phase transition is triggered by the increased motion of the side chains, and the magnitude of the intermolecular side chain packing forces dictate if the transitions occur cooperatively (observed isosbestic point) or as isolated events. Comparison with the 3

  2. Relationship of quantitative structure and pharmacokinetics in fluoroquinolone antibacterials

    PubMed Central

    Cheng, Die; Xu, Wei-Ren; Liu, Chang-Xiao

    2007-01-01

    AIM: To study the relationship between quantitative structure and pharmacokinetics (QSPkR) of fluoroquinolone antibacterials. METHODS: The pharmacokinetic (PK) parameters of oral fluoroquinolones were collected from the litera-ture. These pharmacokinetic data were averaged, 19 compounds were used as the training set, and 3 served as the test set. Genetic function approximation (GFA) module of Cerius2 software was used in QSPkR analysis. RESULTS: A small volume and large polarizability and surface area of substituents at C-7 contribute to a large area under the curve (AUC) for fluoroquinolones. Large polarizability and small volume of substituents at N-1 contribute to a long half life elimination. CONCLUSION: QSPkR models can contribute to some fluoroquinolones antibacterials with excellent pharmacokinetic properties. PMID:17552035

  3. Quantitative Structure-Antifungal Activity Relationships for cinnamate derivatives.

    PubMed

    Saavedra, Laura M; Ruiz, Diego; Romanelli, Gustavo P; Duchowicz, Pablo R

    2015-12-01

    Quantitative Structure-Activity Relationships (QSAR) are established with the aim of analyzing the fungicidal activities of a set of 27 active cinnamate derivatives. The exploration of more than a thousand of constitutional, topological, geometrical and electronic molecular descriptors, which are calculated with Dragon software, leads to predictions of the growth inhibition on Pythium sp and Corticium rolfsii fungi species, in close agreement to the experimental values extracted from the literature. A set containing 21 new structurally related cinnamate compounds is prepared. The developed QSAR models are applied to predict the unknown fungicidal activity of this set, showing that cinnamates like 38, 28 and 42 are expected to be highly active for Pythium sp, while this is also predicted for 28 and 34 in C. rolfsii. PMID:26410195

  4. Quantitative relationships between soil macropore characteristics and preferential flow and transport

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Quantitative relationships between soil structure, especially macropore characteristics, and soil hydraulic properties are essential to improving our ability to predict flow and transport in structured soils. The objectives of this study were to quantitatively relate macropore characteristics to sat...

  5. Investigation of the structure/property relationship of spray-formed 7XXX series high-strength aluminum alloys and their metal matrix composites

    NASA Astrophysics Data System (ADS)

    Sharma-Judd, Malavika M.

    2000-12-01

    The purpose of this investigation was to identify the structure/property relationship of spray formed 7XXX series alloys. High solute, ultra-high strength 7XXX series aluminum alloys with solute contents close to equilibrium solid solubility limits of the Al-Zn-Mg-Cu system have been produced by rapid solidification using spray deposition. The process yields massive preforms directly from the liquid state. Various elements, including chromium, manganese, silver, zirconium and scandium, were incorporated to produce a variety of microstructures and mechanical properties. SiC particulate was added to these same alloy compositions to produce metal matrix composites (MMCs). The resulting extruded products in the T6 and T7 conditions were evaluated and compared. Under peak-aged conditions in the unreinforced materials, strengths in excess of 860 MPa were achieved, with one alloy exceeding 900 MPa. Apart from the elongation to failure, the mechanical properties of the composite materials were equal to or superior to those of their unreinforced counterparts. The superior strength properties of the spray formed alloys were attributed to two major substructures with different scale; nanometer sized eta ' metastable precipitates and slightly larger, but finely distributed dispersoids. The large volume fraction of plate-like eta' precipitates (average size 58A, ranging up to 73 A in diameter) were identified as having a hexagonal structure with lattice parameters a = 0.488 nm and c = 1.376. The remarkable strengthening is predominantly attributed to precipitation hardening. The enhanced mechanical properties of the MMC materials are attributed to the increased dislocation density, and thus, a higher concentration of structural particles compared to the unreinforced materials. Higher gas-to-metal ratios of 4.45, as opposed to lower gas-to-metal ratios of 1.95 produced a refined grain structure with an evenly distributed second phase. In both unreinforced and MMC materials

  6. The effects of high energy electron beam irradiation in air on accelerated aging and on the structure property relationships of low density polyethylene

    NASA Astrophysics Data System (ADS)

    Murray, Kieran A.; Kennedy, James E.; McEvoy, Brian; Vrain, Olivier; Ryan, Damien; Cowman, Richard; Higginbotham, Clement L.

    2013-02-01

    The response of low density polyethylene (LDPE) to high energy electron beam irradiation in air (10 MeV) between 25 and 400 kGy was examined and compared to non-irradiated polyethylene in terms of the mechanical and structural properties. To quantify the degree of crosslinking, swelling studies were performed and from this it was observed that the crosslink density increased as the irradiation dose increased. Furthermore, a reduction was observed in the numerical data for molar mass between adjacent crosslinks and the number of monomeric units between adjacent crosslinks as the irradiation dose was conducted incrementally. Accelerated aging provided evidence that radicals became trapped in the polymer matrix of LDPE and this in turn initiated further reactions to transpire as time elapsed, leading to additional alteration in the structural properties. Fourier transform infrared spectroscopy (FTIR) was implemented to provide insight into this. This technique established that the aging process had increased the oxidative degradation products due to oxygen permeation into the polymer and double bonds within the material. Mechanical testing revealed an increase in the tensile strength and a decrease in the elongation at break. Accelerated aging caused additional modifications to occur in the mechanical properties which are further elucidated throughout this study. Dynamic frequency sweeps investigated the effects of irradiation on the structural properties of LDPE. The effect of varying the irradiation dose concentration was apparent as this controlled the level of crosslinking within the material. Maxwell and Kelvin or Voigt models were employed in this analytical technique to define the reaction procedure of the frequency sweep test with regards to non-crosslinked and crosslinked LDPE.

  7. Misconceived Relationships between Logical Positivism and Quantitative Research: An Analysis in the Framework of Ian Hacking.

    ERIC Educational Resources Information Center

    Yu, Chong Ho

    Although quantitative research methodology is widely applied by psychological researchers, there is a common misconception that quantitative research is based on logical positivism. This paper examines the relationship between quantitative research and eight major notions of logical positivism: (1) verification; (2) pro-observation; (3)…

  8. Quantitative structure-activity relationships for organophosphates binding to acetylcholinesterase.

    PubMed

    Ruark, Christopher D; Hack, C Eric; Robinson, Peter J; Anderson, Paul E; Gearhart, Jeffery M

    2013-02-01

    Organophosphates are a group of pesticides and chemical warfare nerve agents that inhibit acetylcholinesterase, the enzyme responsible for hydrolysis of the excitatory neurotransmitter acetylcholine. Numerous structural variants exist for this chemical class, and data regarding their toxicity can be difficult to obtain in a timely fashion. At the same time, their use as pesticides and military weapons is widespread, which presents a major concern and challenge in evaluating human toxicity. To address this concern, a quantitative structure-activity relationship (QSAR) was developed to predict pentavalent organophosphate oxon human acetylcholinesterase bimolecular rate constants. A database of 278 three-dimensional structures and their bimolecular rates was developed from 15 peer-reviewed publications. A database of simplified molecular input line entry notations and their respective acetylcholinesterase bimolecular rate constants are listed in Supplementary Material, Table I. The database was quite diverse, spanning 7 log units of activity. In order to describe their structure, 675 molecular descriptors were calculated using AMPAC 8.0 and CODESSA 2.7.10. Orthogonal projection to latent structures regression, bootstrap leave-random-many-out cross-validation and y-randomization were used to develop an externally validated consensus QSAR model. The domain of applicability was assessed by the William's plot. Six external compounds were outside the warning leverage indicating potential model extrapolation. A number of compounds had residuals >2 or <-2, indicating potential outliers or activity cliffs. The results show that the HOMO-LUMO energy gap contributed most significantly to the binding affinity. A mean training R (2) of 0.80, a mean test set R (2) of 0.76 and a consensus external test set R (2) of 0.66 were achieved using the QSAR. The training and external test set RMSE values were found to be 0.76 and 0.88. The results suggest that this QSAR model can be used in

  9. Quantitative structure toxicity relationships for phenols in isolated rat hepatocytes.

    PubMed

    Moridani, Majid Y; Siraki, Arno; O'Brien, Peter J

    2003-05-01

    Quantitative structure toxicity relationship (QSTR) equations were obtained to predict and describe the cytotoxicity of 31 phenols using logLD(50) as a concentration to induce 50% cytotoxicity of isolated rat hepatocytes in 2 h and logP as octanol/water partitioning: logLD(50) (microM)=-0.588(+/-0.059)logP+4.652(+/-0.153) (n=27, r(2)=0.801, s=0.261, P<1 x 10(-9)). Hydroquinone, catechol, 4-nitrophenol, and 2,4-dinitrophenol were outliers for this equation. When the ionization constant pK(a) was considered as a contributing factor a two-parameter QSTR equation was derived: logLD(50) (microM)=-0.595(+/-0.051)logP+0.197(+/-0.029)pK(a)+2.665(+/-0.281) (n=28, r(2)=0.859, s=0.218, P<1 x 10(-6)). Using sigma+, the Brown variation of the Hammet electronic constant, as a contributing parameter, the cytotoxicity of phenols towards hepatocytes were defined by logLD(50) (microM)=-0.594(+/-0.052)logP-0.552(+/-0.085)sigma+ +4.540(+/-0.132) (n=28, r(2)=0.853, s=0.223, P<1 x 10(-6)). Replacing sigma+ with the homolytic bond dissociation energy (BDE) for (X-PhOH+PhO.-->X-PhO.+PhOH) led to logLD(50) (microM)=-0.601(+/-0.066)logP-0.040(+/-0.018)BDE+4.611(+/-0.166) (n=23, r(2)=0.827, s=0.223, P<0.05). Hydroquinone, catechol and 2-nitrophenol were outliers for the above equations. Using redox potential and logP led to a new correlation: logLD(50) (microM)=-0.529(+/-0.135)logP+2.077(+/-0.892)E(p/2)+2.806(+/-0.592) (n=15, r(2)=0.561, s=0.383, P<0.05) with 4-nitrophenol as an outlier. Our findings indicate that phenols with higher lipophilicity, BDE, or sigma+ values or with lower pK(a) and redox potential were more toxic towards hepatocytes. We also showed that a collapse of hepatocyte mitochondrial membrane potential preceded the cytotoxicity of most phenols. Our study indicates that one or a combination of mechanisms; i.e. mitochondrial uncoupling, phenoxy radicals, or phenol metabolism to quinone methides and quinones, contribute to phenol cytotoxicity towards hepatocytes depending on

  10. PREDICTING TOXICOLOGICAL ENDPOINTS OF CHEMICALS USING QUANTITATIVE STRUCTURE-ACTIVITY RELATIONSHIPS (QSARS)

    EPA Science Inventory

    Quantitative structure-activity relationships (QSARs) are being developed to predict the toxicological endpoints for untested chemicals similar in structure to chemicals that have known experimental toxicological data. Based on a very large number of predetermined descriptors, a...

  11. Quantitative Structure--Activity Relationship Modeling of Rat Acute Toxicity by Oral Exposure

    EPA Science Inventory

    Background: Few Quantitative Structure-Activity Relationship (QSAR) studies have successfully modeled large, diverse rodent toxicity endpoints. Objective: In this study, a combinatorial QSAR approach has been employed for the creation of robust and predictive models of acute toxi...

  12. Thermodynamics of the hydrogen bonding of nitrogen-containing cyclic and aromatic compounds with proton donors: The structure-property relationship

    NASA Astrophysics Data System (ADS)

    Rakipov, I. T.; Varfolomeev, M. A.; Kirgizov, A. Yu.; Solomonov, B. N.

    2014-12-01

    Enthalpies of dissolution are measured at infinite dilution of nitrogen-containing cyclic (pyrrolidine, piperidine) and aromatic compounds (aniline, N-methylaniline, N,N-dimethylaniline, N-methylimidazole, pyridine, 2-, 3-, 4-methylpyridine, pyrrole, N-methylpyrrole) in chloroform and dichloromethane, and vice versa ( T = 298.15 K). The enthalpies of hydrogen bonds in the above systems are calculated. Relationships between resulting thermochemical data and the structure of nitrogen-containing cyclic and aromatic compounds are explored.

  13. Structure-Property Relationships in CO2-philic (Co)polymers: Phase Behavior, Self-Assembly, and Stabilization of Water/CO2 Emulsions.

    PubMed

    Girard, Etienne; Tassaing, Thierry; Marty, Jean-Daniel; Destarac, Mathias

    2016-04-13

    This Review provides comprehensive guidelines for the design of CO2-philic copolymers through an exhaustive and precise coverage of factors governing the solubility of different classes of polymers. Starting from computational calculations describing the interactions of CO2 with various functionalities, we describe the phase behavior in sc-CO2 of the main families of polymers reported in literature. The self-assembly of amphiphilic copolymers of controlled architecture in supercritical carbon dioxide and their use as stabilizers for water/carbon dioxide emulsions then are covered. The relationships between the structure of such materials and their behavior in solutions and at interfaces are systematically underlined throughout these sections. PMID:27014998

  14. Quantitative relationship of sick building syndrome symptoms with ventilation rates

    SciTech Connect

    Fisk, William J.; Mirer, Anna G.; Mendell, Mark J.

    2009-01-01

    Data from published studies were combined and analyzed to develop best-fit equations and curves quantifying the change in sick building syndrome (SBS) symptom prevalence in office workers with ventilation rate. For each study, slopes were calculated, representing the fractional change in SBS symptom prevalence per unit change in ventilation rate per person. Values of ventilation rate, associated with each value of slope, were also calculated. Linear regression equations were fitted to the resulting data points, after weighting by study size. Integration of the slope-ventilation rate equations yielded curves of relative SBS symptom prevalence versus ventilation rate. Based on these analyses, as the ventilation rate drops from 10 to 5 L/s-person, relative SBS symptom prevalence increases approximately 23percent (12percent to 32percent), and as ventilation rate increases from 10 to 25 L/s-person, relative prevalence decreases approximately 29percent (15percent to 42percent). Variations in SBS symptom types, building features, and outdoor air quality may cause the relationship ofSBS symptom prevalence with ventilation rate in specific situations to differ from the average relationship predicted in this paper.

  15. Structure-property relationships of a class of carbamate-based Fatty Acid Amide Hydrolase (FAAH) inhibitors: chemical and biological stability

    PubMed Central

    Vacondio, Federica; Silva, Claudia; Lodola, Alessio; Fioni, Alessandro; Rivara, Silvia; Duranti, Andrea; Tontini, Andrea; Sanchini, Silvano; Clapper, Jason; Piomelli, Daniele; Tarzia, Giorgio

    2012-01-01

    Cyclohexylcarbamic acid aryl esters are a class of Fatty Acid Amide Hydrolase (FAAH) inhibitors, which includes the reference compound URB597. The reactivity of their carbamate fragment is involved in pharmacological activity and may affect pharmacokinetic and toxicological properties. We conducted in vitro stability experiments in chemical and biological environments to investigate the structure-stability relationships in this class of compounds. The results show that electrophilicity of the carbamate influences its chemical stability, as suggested by the relation between the rate constant of alkaline hydrolysis (log kpH9) and the energy of lowest unoccupied molecular orbital (LUMO). Introduction of small, electron donor substituents at conjugated positions of the O-aryl moiety increased overall hydrolytic stability of the carbamate group without affecting FAAH inhibitory potency, whereas peripheral nonconjugated hydrophilic groups, which favor FAAH recognition, helped reducing oxidative metabolism in the liver. PMID:19554599

  16. Quantitative Relationships Between Microdamage and Cancellous Bone Strength and Stiffness

    PubMed Central

    Hernandez, C.J.; Lambers, F.M.; Widjaja, J.; Chapa, C.; Rimnac, C.M.

    2014-01-01

    Microscopic tissue damage (microdamage) is an aspect of bone quality associated with impaired bone mechanical performance. While it is clear that bone tissue submitted to more severe loading has greater amounts of microdamage (as measured through staining), how microdamage influences future mechanical performance of bone has not been well studied, yet is necessary for understanding the mechanical consequences of the presence of microdamage. Here we determine how stained microdamage generated by a single compressive overload affects subsequent biomechanical performance of cancellous bone. Human vertebral cancellous bone specimens (n = 47) from 23 donors (14 male, 9 female, 64–92 years of age) were submitted to a compressive overload, stained for microdamage, then reloaded in compression to determine the relationship between the amount of microdamage caused by the initial load and reductions in mechanical performance during the reload. Damage volume fraction (DV/BV) caused by the initial overload was related to reductions in Young’s modulus, yield strength, ultimate strength, and yield strain upon reloading (p < 0.05, R2 = 0.18–0.34). The regression models suggest that, on average, relatively small amounts of microdamage are associated with large reductions in reload mechanical properties: a 1.50% DV/BV caused by a compressive overload was associated with an average reduction in Young’s modulus of 41.0 ± 3.2 % (mean ± SE), an average reduction in yield strength of 63.1 ± 4.5% and an average reduction in ultimate strength of 52.7 ± 4.0%. Specimens loaded beyond 1.2% (1.2–4.0% apparent strain) demonstrated a single relationship between reload mechanical properties (Young’s modulus, yield strength, and ultimate strength) and bone volume fraction despite a large range in amounts of microdamage. Hence, estimates of future mechanical performance of cancellous bone can be achieved using the bone volume fraction and whether or not a specimen was previously

  17. Improving quantitative structure-activity relationships through multiobjective optimization.

    PubMed

    Nicolotti, Orazio; Giangreco, Ilenia; Miscioscia, Teresa Fabiola; Carotti, Angelo

    2009-10-01

    A multiobjective optimization algorithm was proposed for the automated integration of structure- and ligand-based molecular design. Driven by a genetic algorithm, the herein proposed approach enabled the detection of a number of trade-off QSAR models accounting simultaneously for two independent objectives. The first was biased toward best regressions among docking scores and biological affinities; the second minimized the atom displacements from a properly established crystal-based binding topology. Based on the concept of dominance, 3D QSAR equivalent models profiled the Pareto frontier and were, thus, designated as nondominated solutions of the search space. K-means clustering was, then, operated to select a representative subset of the available trade-off models. These were effectively subjected to GRID/GOLPE analyses for quantitatively featuring molecular determinants of ligand binding affinity. More specifically, it was demonstrated that a) diverse binding conformations occurred on the basis of the ligand ability to profitably contact different part of protein binding site; b) enzyme selectivity was better approached and interpreted by combining diverse equivalent models; and c) trade-off models were successful and even better than docking virtual screening, in retrieving at high sensitivity active hits from a large pool of chemically similar decoys. The approach was tested on a large series, very well-known to QSAR practitioners, of 3-amidinophenylalanine inhibitors of thrombin and trypsin, two serine proteases having rather different biological actions despite a high sequence similarity. PMID:19785453

  18. Excited States and Photodebromination of Selected Polybrominated Diphenyl Ethers: Computational and Quantitative Structure—Property Relationship Studies

    PubMed Central

    Luo, Jin; Hu, Jiwei; Wei, Xionghui; Li, Lingyun; Huang, Xianfei

    2015-01-01

    This paper presents a density functional theory (DFT)/time-dependent DFT (TD-DFT) study on the lowest lying singlet and triplet excited states of 20 selected polybrominateddiphenyl ether (PBDE) congeners, with the solvation effect included in the calculations using the polarized continuum model (PCM). The results obtained showed that for most of the brominated diphenyl ether (BDE) congeners, the lowest singlet excited state was initiated by the electron transfer from HOMO to LUMO, involving a π–σ* excitation. In triplet excited states, structure of the BDE congeners differed notably from that of the BDE ground states with one of the specific C–Br bonds bending off the aromatic plane. In addition, the partial least squares regression (PLSR), principal component analysis-multiple linear regression analysis (PCA-MLR), and back propagation artificial neural network (BP-ANN) approaches were employed for a quantitative structure-property relationship (QSPR) study. Based on the previously reported kinetic data for the debromination by ultraviolet (UV) and sunlight, obtained QSPR models exhibited a reasonable evaluation of the photodebromination reactivity even when the BDE congeners had same degree of bromination, albeit different patterns of bromination. PMID:25569092

  19. Development of Quantitative Structure-Activity Relationship Models for Predicting Chronic Toxicity of Substituted Benzenes to Daphnia Magna.

    PubMed

    Fan, Deling; Liu, Jining; Wang, Lei; Yang, Xianhai; Zhang, Shenghu; Zhang, Yan; Shi, Lili

    2016-05-01

    The chronic toxicity of anthropogenic molecules such as substituted benzenes to Daphnia magna is a basic eco-toxicity parameter employed to assess their environmental risk. As the experimental methods are laborious, costly, and time-consuming, development in silico models for predicting the chronic toxicity is vitally important. In this study, on the basis of five molecular descriptors and 48 compounds, a quantitative structure-property relationship model that can predict the chronic toxicity of substituted benzenes were developed by employing multiple linear regressions. The correlation coefficient (R (2)) and root-mean square error (RMSE) for the training set were 0.836 and 0.390, respectively. The developed model was validated by employing 10 compounds tested in our lab. The R EXT (2) and RMSE EXT for the validation set were 0.736 and 0.490, respectively. To further characterizing the toxicity mechanism of anthropogenic molecules to Daphnia, comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) models were developed. PMID:27016939

  20. Quantitative structure-(chromatographic) retention relationship models for dissociating compounds.

    PubMed

    Kubik, Łukasz; Wiczling, Paweł

    2016-08-01

    The aim of this work was to develop mathematical models relating the hydrophobicity and dissociation constant of an analyte with its structure, which would be useful in predicting analyte retention times in reversed-phase liquid chromatography. For that purpose a large and diverse group of 115 drugs was used to build three QSRR models combining retention-related parameters (logkw-chromatographic measure of hydrophobicity, S-slope factor from Snyder-Soczewinski equation, and pKa) with structural descriptors calculated by means of molecular modeling for both dissociated and nondissociated forms of analytes. Lasso, Stepwise and PLS regressions were used to build statistical models. Moreover a simple QSRR equations based on lipophilicity and dissociation constant parameters calculated in the ACD/Labs software were proposed and compared with quantum chemistry-based QSRR equations. The obtained relationships were further used to predict chromatographic retention times. The predictive performances of the obtained models were assessed using 10-fold cross-validation and external validation. The QSRR equations developed were simple and were characterized by satisfactory predictive performance. Application of quantum chemistry-based and ACD-based descriptors leads to similar accuracy of retention times' prediction. PMID:26960942

  1. Synthesis-atomic structure-properties relationships in metallic nanoparticles by total scattering experiments and 3D computer simulations: case of Pt-Ru nanoalloy catalysts.

    PubMed

    Prasai, Binay; Ren, Yang; Shan, Shiyao; Zhao, Yinguang; Cronk, Hannah; Luo, Jin; Zhong, Chuan-Jian; Petkov, Valeri

    2015-05-01

    observed enhancement of the catalytic activity of PtxRu100-x alloy NPs at x ∼ 50. Implications of so-established relationships between the atomic structure and catalytic activity of Pt-Ru alloy NPs on efforts aimed at improving further the latter by tuning-up the former are discussed and the usefulness of detailed NP structure studies to advancing science and technology of metallic NPs - exemplified. PMID:25874741

  2. Synthesis-atomic structure-properties relationships in metallic nanoparticles by total scattering experiments and 3D computer simulations: case of Pt-Ru nanoalloy catalysts

    NASA Astrophysics Data System (ADS)

    Prasai, Binay; Ren, Yang; Shan, Shiyao; Zhao, Yinguang; Cronk, Hannah; Luo, Jin; Zhong, Chuan-Jian; Petkov, Valeri

    2015-04-01

    observed enhancement of the catalytic activity of PtxRu100-x alloy NPs at x ~ 50. Implications of so-established relationships between the atomic structure and catalytic activity of Pt-Ru alloy NPs on efforts aimed at improving further the latter by tuning-up the former are discussed and the usefulness of detailed NP structure studies to advancing science and technology of metallic NPs - exemplified.An approach to determining the 3D atomic structure of metallic nanoparticles (NPs) in fine detail and using the unique knowledge obtained for rationalizing their synthesis and properties targeted for optimization is described and exemplified on Pt-Ru alloy NPs of importance to the development of devices for clean energy conversion such as fuel cells. In particular, PtxRu100-x alloy NPs, where x = 31, 49 and 75, are synthesized by wet chemistry and activated catalytically by a post-synthesis treatment involving heating under controlled N2-H2 atmosphere. So-activated NPs are evaluated as catalysts for gas-phase CO oxidation and ethanol electro-oxidation reactions taking place in fuel cells. Both as-synthesized and activated NPs are characterized structurally by total scattering experiments involving high-energy synchrotron X-ray diffraction coupled to atomic pair distribution functions (PDFs) analysis. 3D structure models both for as-synthesized and activated NPs are built by molecular dynamics simulations based on the archetypal for current theoretical modelling Sutton-Chen method. Models are refined against the experimental PDF data by reverse Monte Carlo simulations and analysed in terms of prime structural characteristics such as metal-to-metal bond lengths, bond angles and first coordination numbers for Pt and Ru atoms. Analysis indicates that, though of a similar type, the atomic structure of as-synthesized and respective activated NPs differ in several details of importance to NP catalytic properties. Structural characteristics of activated NPs and data for their catalytic

  3. Quantitative determination based on the differences between spectra-temperature relationships.

    PubMed

    Li, Zhe; Zhou, Mei; Luo, Yongshun; Li, Gang; Lin, Ling

    2016-08-01

    In the Near-infrared (NIR) spectral measurement it is not always possible to keep the experimental conditions constant. The fluctuations in external variables, such as temperature, will result in a nonlinear shift and a broadening of the spectral bands. In this study, the temperature-induced spectral variation coefficient (TSVC) was obtained by using loading space standardization (LSS). The relationship between TSVC and normalized squared temperature was quantitatively analyzed and applied to the quantitative determination of the compositions in mixtures. NIR spectra of peanut-soy-corn oil mixtures measured at seven temperatures were analyzed. It was found that, the relationship between TSVC and normalized squared temperature can be established by using LSS. Furthermore, the quantitative determination of the compositions in a mixture can be achieved by using the difference between the relationships, i.e., the slope of the relationship. The calibration curves between slope and composition volume are found to be reliable with the correlation coefficients (R(2)) as high as 0.9992. Quantitative determination by the calibration curves were also validated. Therefore, the method can be an effective tool for investigating the effect of temperature and quantitatively analysis. PMID:27216655

  4. [Quantitative structure activity relationship models based on heuristic method and gene expression programming for the prediction of the pK(a) values of sulfa drugs].

    PubMed

    Li, Yu-qin; Si, Hong-zong; Xiao, Yu-liang; Liu, Cai-hong; Xia, Cheng-cai; Li, Ke; Qi, Yong-xiu

    2009-05-01

    Quantitative structure-property relationships (QSPR) were developed to predict the pK(a) values of sulfa drugs via heuristic method (HM) and gene expression programming (GEP). The descriptors of 31 sulfa drugs were calculated by the software CODESSA, which can calculate constitutional, topological, geometrical, electrostatic, and quantum chemical descriptors. HM was also used for the preselection of 4 appropriate molecular descriptors. Linear and nonlinear QSPR models were developed based on the HM and GEP separately and two prediction models lead to a good correlation coefficient (R) of 0.90 and 0.95. The two QSPR models are tseful in predicting pK(a) during the discovery of new drugs and providing theory information for studying the new drugs. PMID:19618723

  5. THREE-DIMENSIONAL QUANTITATIVE STRUCTURE-PROPERTY RELATIONSHIP (3D-QSPR) MODELS FOR PREDICTION OF THERMODYNAMIC PROPERTIES OF POLYCHLORINATED BIPHENYLS (PCBS): ENTHALPY OF SUBLIMATION. (R826133)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  6. THREE-DIMENSIONAL QUANTITATIVE STRUCTURE-PROPERTY RELATIONSHIP (3D-QSPR) MODELS FOR PREDICTION OF THERMODYNAMIC PROPERTIES OF POLYCHLORINATED BIPHENYLS (PCBS): ENTHALPY OF VAPORIZATION. (R826133)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  7. Structure-property relationships of carbon aerogels

    SciTech Connect

    Pekala, R.W.; Alviso, C.T.; Kong, F.M.

    1993-12-01

    Of the organic reactions in sol-gel polymerizations, the most studied reaction is the aqueous polycondensation of resorcinol with formaldehyde; the resulting crosslinked gels are supercritically dried from CO{sub 2} to give resorcinol-formaldehyde (RF) aerogels. These aerogels can be pyrolyzed to form vitreous carbon monoliths with black color, high porosity, ultrafine cell/pore size, high surface area, and interconnected particles of the organic precursor. The structure and properties of the carbon aerogels depend on R/C (resorcinol/catalyst) ratio of starting solution, pyrolysis temperature, and chemical activation. Each variable is discussed. Carbon aerogels provide an almost ideal electrode material (in double-layer capacitors) owing to low electrical resistivity (<40 mohm-cm), controllable pore size distribution (5--500 {angstrom}), and high volumetric surface areas ({approximately}500 m{sup 2}/cm{sup 3}).

  8. Structure-property relationships in semiconductor alloys

    NASA Technical Reports Server (NTRS)

    Sher, A.; Berding, M. A.; Krishnamurthy, S.; Van Schilfgaarde, M.; Chen, A.-B.

    1987-01-01

    It is presently noted that the atomic distribution of constituents in semiconductor alloys is never truly random, since there are always interactions giving rise to correlations whose degree and character depend on which interactions are dominant, as well as on the growth conditions. Although most of the interactions that can be expected to generate correlations have been identified, the fact that not all have been thus far treated exhaustively leaves several details unclear. A characterization of the primary effects in general terms is accordingly achieved.

  9. A Quantitative Exploration of the Relationship between Patient Health and Electronic Personal Health Records

    ERIC Educational Resources Information Center

    Hines, Denise Williams

    2009-01-01

    The use of electronic personal health records is becoming increasingly more popular as healthcare providers, healthcare and government leaders, and patients are seeking ways to improve healthcare quality and to decrease costs (Abrahamsen, 2007). This quantitative, descriptive correlational study examined the relationship between the degree of…

  10. A Quantitative Study of the Relationship between Leadership Practice and Strategic Intentions to Use Cloud Computing

    ERIC Educational Resources Information Center

    Castillo, Alan F.

    2014-01-01

    The purpose of this quantitative correlational cross-sectional research study was to examine a theoretical model consisting of leadership practice, attitudes of business process outsourcing, and strategic intentions of leaders to use cloud computing and to examine the relationships between each of the variables respectively. This study…

  11. QUANTITATIVE STRUCTURE-ACTIVITY RELATIONSHIPS FOR CHEMICAL REDUCTIONS OF ORGANIC CONTAMINANTS

    EPA Science Inventory

    Sufficient kinetic data on abiotic reduction reactions involving organic contaminants are now available that quantitative structure-activity relationships (QSARs) for these reactions can be developed. Over 50 QSARs have been reported, most in just the last few years, and they ar...

  12. Quantitative Causal-Comparative Relationship between Interactive Whiteboard Instruction and Student Science Proficiency

    ERIC Educational Resources Information Center

    Danelczyk, Ewa Krystyna

    2013-01-01

    The purpose of this quantitative causal-comparative study was to investigate the relationship between the instructional effects of the interactive whiteboard and students' proficiency levels in eighth-grade science as evidenced by the state FCAT scores. A total of 46 eighth-grade science teachers in a South Florida public school district completed…

  13. Implementing Response to Intervention in Title I Elementary Schools: A Quantitative Study of Teacher Response Relationships

    ERIC Educational Resources Information Center

    Webster, Katina F.

    2012-01-01

    General educators and special educators in Title I elementary schools perceive the relationships between principles of RTI and their state RTI framework, the implementation of RTI, and professional development received in RTI differently. A quantitative survey-based research methodology was employed including the use of Cronbach's alpha to…

  14. An investigation of the structure-property relationships in ionic polymer polymer composites (IP2Cs) manufactured by polymerization in situ of PEDOT/PSS on Nafion®117

    NASA Astrophysics Data System (ADS)

    Di Pasquale, G.; Graziani, S.; Messina, F. G.; Pollicino, A.; Puglisi, R.; Umana, E.

    2014-03-01

    Ionic polymer polymer composites (IP2Cs) are all-organic electroactive polymers (EAPs) that show sensing and actuation capabilities when a deformation or a voltage is applied, respectively. They are fabricated starting from an ionic polymer coated on both sides with a conducting polymer as electrode element. In this work, poly(3,4-ethylendioxytiophene)-poly-(styrenesulfonate) (PEDOT/PSS) has been polymerized directly on Nafion®117 membrane and devices have been manufactured varying the polymerization time. Water and ethylene glycol (EG) have been used as solvents. The obtained IP2Cs have been characterized using thermal and mechanical analyses and electromechanically tested. The results have shown that in IP2Cs manufactured by polymerization in situ the PEDOT/PSS layer adheres very strongly on the Nafion®117 film, improving the possibility of rehydrating the devices after use. Moreover, taking into account that the different polymerization times influence the uniformity of the surface of the organic electrode and, consequently, both device stiffness and electrode conductivity, the structure-property relationships of the obtained devices have been investigated. The influence of the different solvents inside the devices has also been studied when IP2Cs have been used as actuators or sensors. Reported results show that it is possible to modulate the performances of IP2Cs by varying some manufacture parameters and the solvent.

  15. Stationary phases with special structural properties for high-throughput separation techniques: preparation, characterization and applications.

    PubMed

    Buszewski, Boguslaw; Welerowicz, Tomasz

    2004-06-01

    Stationary phases with specific structural properties for high-throughput liquid chromatographic (LC) techniques are described. Special attention was paid to phases with special structural properties, mainly containing internal functional group (e.g. amide). Such materials are generally called "embedded phases". There are phases created in amidation process of aminopropylated silica gel, especially phases based on biological compounds, like phospholipids and cholesterol, which are called immobilized artificial membranes (IAM's). The synthesis and applications of polar embedded amide LC stationary phases were also reviewed. Methods of characterization of synthesized packing materials were presented, with general focusing on spectroscopic measurements like (13C and 29Si CP/MAS NMR and FT-IR), elemental and thermal analysis as well as chromatographic quantitative structure-retention relationships (QSRR) and extended chemometric tests. The potential applications of various dedicated stationary phases in a high-throughput LC screening procedures were also presented. PMID:15200378

  16. Semiconductor alloys - Structural property engineering

    NASA Technical Reports Server (NTRS)

    Sher, A.; Van Schilfgaarde, M.; Berding, M.; Chen, A.-B.

    1987-01-01

    Semiconductor alloys have been used for years to tune band gaps and average bond lengths to specific applications. Other selection criteria for alloy composition, and a growth technique designed to modify their structural properties, are presently considered. The alloys Zn(1-y)Cd(y)Te and CdSe(y)Te(1-y) are treated as examples.

  17. Molecular-Level Control of Ciclopirox Olamine Release from Poly(ethylene oxide)-Based Mucoadhesive Buccal Films: Exploration of Structure-Property Relationships with Solid-State NMR.

    PubMed

    Urbanova, Martina; Gajdosova, Marketa; Steinhart, Miloš; Vetchy, David; Brus, Jiri

    2016-05-01

    polymorphic form, Form I, which exhibited reduced dissolution kinetics. The bioavailability of CPX olamine formulated as PEO-based MBFs can thus be effectively controlled by inducing the complete dispersion and/or microsegregation and nanocrystallization of CPX olamine in the polymer matrix. Solid-state NMR spectroscopy is an efficient tool for exploring structure-property relationships in these complex pharmaceutical solids. PMID:27019088

  18. Trophic relationships in an estuarine environment: A quantitative fatty acid analysis signature approach

    NASA Astrophysics Data System (ADS)

    Magnone, Larisa; Bessonart, Martin; Gadea, Juan; Salhi, María

    2015-12-01

    In order to better understand the functioning of aquatic environments, it is necessary to obtain accurate diet estimations in food webs. Their description should incorporate information about energy flow and the relative importance of trophic pathways. Fatty acids have been extensively used in qualitative studies on trophic relationships in food webs. Recently a new method to estimate quantitatively single predator diet has been developed. In this study, a model of aquatic food web through quantitative fatty acid signature analysis was generated to identify the trophic interactions among the species in the Rocha Lagoon. The biological sampling over two consecutive annual periods was comprehensive enough to identify all functional groups in the aquatic food web (except birds and mammals). Heleobia australis seemed to play a central role in this estuarine ecosystem. As both, a grazer and a prey to several other species, probably H. australis is transferring a great amount of energy to upper trophic levels. Most of the species at Rocha Lagoon have a wide range of prey items in their diet reflecting a complex food web, which is characteristic of extremely dynamic environment as estuarine ecosystems. QFASA is a model in tracing and quantitative estimate trophic pathways among species in an estuarine food web. The results obtained in the present work are a valuable contribution in the understanding of trophic relationships in Rocha Lagoon.

  19. Quantitative genetic models for describing simultaneous and recursive relationships between phenotypes.

    PubMed Central

    Gianola, Daniel; Sorensen, Daniel

    2004-01-01

    Multivariate models are of great importance in theoretical and applied quantitative genetics. We extend quantitative genetic theory to accommodate situations in which there is linear feedback or recursiveness between the phenotypes involved in a multivariate system, assuming an infinitesimal, additive, model of inheritance. It is shown that structural parameters defining a simultaneous or recursive system have a bearing on the interpretation of quantitative genetic parameter estimates (e.g., heritability, offspring-parent regression, genetic correlation) when such features are ignored. Matrix representations are given for treating a plethora of feedback-recursive situations. The likelihood function is derived, assuming multivariate normality, and results from econometric theory for parameter identification are adapted to a quantitative genetic setting. A Bayesian treatment with a Markov chain Monte Carlo implementation is suggested for inference and developed. When the system is fully recursive, all conditional posterior distributions are in closed form, so Gibbs sampling is straightforward. If there is feedback, a Metropolis step may be embedded for sampling the structural parameters, since their conditional distributions are unknown. Extensions of the model to discrete random variables and to nonlinear relationships between phenotypes are discussed. PMID:15280252

  20. Quantitative analysis of saltwater-freshwater relationships in groundwater systems-A historical perspective

    USGS Publications Warehouse

    Reilly, T.E.; Goodman, A.S.

    1985-01-01

    Although much progress has been made toward the mathematical description of saltwater-freshwater relationships in groundwater systems since the late 19th century, the advective and dispersive mechanisms involved are still incompletely understood. This article documents the major historical advances in this subject and summarizes the major direction of current studies. From the time of Badon Ghyben and Herzberg, it has been recognized that density is important in mathematically describing saltwater-freshwater systems. Other mechanisms, such as hydrodynamic dispersion, were identified later and are still not fully understood. Quantitative analysis of a saltwater-freshwater system attempts to mathematically describe the physical system and the important mechanisms using reasonable simplifications and assumptions. This paper, in developing the history of quantitative analysis discusses many of these simplifications and assumptions and their effect on describing and understanding the phenomenon. ?? 1985.

  1. Toxicity challenges in environmental chemicals: Prediction of human plasma protein binding through quantitative structure-activity relationship (QSAR) models

    EPA Science Inventory

    The present study explores the merit of utilizing available pharmaceutical data to construct a quantitative structure-activity relationship (QSAR) for prediction of the fraction of a chemical unbound to plasma protein (Fub) in environmentally relevant compounds. Independent model...

  2. FISH ACUTE TOXICITY SYNDROMES: APPLICATION TO THE DEVELOPMENT OF MECHANISM-SPECIFIC QSARS (QUANTITATIVE STRUCTURE ACTIVITY RELATIONSHIPS)

    EPA Science Inventory

    Predictive models based on quantitative structure activity relationships (QSARs), are used as rapid screening tools to identify potentially hazardous chemicals. Several QSARs are now available that predict the acute toxicity of narcotic-industrial chemicals. Predictions for compo...

  3. ESTIMATION OF MICROBIAL REDUCTIVE TRANSFORMATION RATES FOR CHLORINATED BENZENES AND PHENOLS USING A QUANTITATIVE STRUCTURE-ACTIVITY RELATIONSHIP APPROACH

    EPA Science Inventory

    A set of literature data was used to derive several quantitative structure-activity relationships (QSARs) to predict the rate constants for the microbial reductive dehalogenation of chlorinated aromatics. Dechlorination rate constants for 25 chloroaromatics were corrected for th...

  4. Trunk muscle amplitude-force relationship is only quantitatively influenced by control strategy.

    PubMed

    Hansen, Laura Christin; Anders, Christoph

    2016-02-01

    The Surface EMG (SEMG) amplitude-force relationship of trunk muscles has been shown to be non-linear for the abdominal muscles and linear for the back muscles. Recent studies could prove that abdominal muscles' stress level is influenced by control strategy with higher amplitude levels when the trunk posture has to be maintained along its body axis at defined submaximal force levels (posture-controlled), meanwhile compensating corresponding force levels against a fixed resistance point (force-controlled) in upright position caused inferior amplitude alterations. We wanted to check if the different control strategies alter the amplitude-force relationship of trunk muscles quantitatively and/or qualitatively. In this study 39 healthy subjects of both sexes were investigated while being isometrically exposed to defined submaximal flexion and extension forces on their trunk. The forces were generated by applying real (posture-controlled) and simulated (force-controlled) tilt angles on the trunk. SEMG was taken from five trunk muscles and normalized according to the amplitude during maximum voluntary contractions (MVC normalized), and to the occurring maximum value during every force direction and strategy, respectively (maximum normalized). The MVC normalized amplitudes were always greater for the posture-controlled situations for all abdominal muscles, independent of sex, but were not affected at all for the back muscles. The maximum normalized amplitudes of all trunk muscles were not systematically influenced by the applied control strategy. Therefore, the amplitude-force relationship of trunk muscles is muscle and exercise type-specific: for the abdominal muscles the amplitude-force relationship is quantitatively altered by control strategy. PMID:26777603

  5. Studying the relationship between redox and cell growth using quantitative phase imaging (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Sridharan, Shamira; Leslie, Matthew T.; Bapst, Natalya; Smith, John; Gaskins, H. Rex; Popescu, Gabriel

    2016-03-01

    Quantitative phase imaging has been used in the past to study the dry mass of cells and study cell growth under various treatment conditions. However, the relationship between cellular redox and growth rates has not yet been studied in this context. This study employed the recombinant Glrx-roGFP2 redox biosensor targeted to the mitochondrial matrix or cytosolic compartments of A549 lung epithelial carcinoma cells. The Glrx-roGFP2s biosensor consists of a modified GFP protein containing internal cysteine residues sensitive to the local redox environment. The formation/dissolution of sulfide bridges contorts the internal chromophore, dictating corresponding changes in florescence emission that provide direct measures of the local redox potential. Combining 2-channel florescent imaging of the redox sensor with quantitative phase imaging allowed observation of redox homeostasis alongside measurements of cellular mass during full cycles of cellular division. The results indicate that mitochondrial redox showed a stronger inverse correlation with cell growth than cytoplasmic redox states; although redox changes are restricted to a 5% range. We are now studying the relationship between mitochondrial redox and cell growth in an isogenic series of breast cell lines built upon the MCF-10A genetic background that vary both in malignancy and metastatic potential.

  6. Development and Validation of Quantitative Structure-Activity Relationship Models for Compounds Acting on Serotoninergic Receptors

    PubMed Central

    Żydek, Grażyna; Brzezińska, Elżbieta

    2012-01-01

    A quantitative structure-activity relationship (QSAR) study has been made on 20 compounds with serotonin (5-HT) receptor affinity. Thin-layer chromatographic (TLC) data and physicochemical parameters were applied in this study. RP2 TLC 60F254 plates (silanized) impregnated with solutions of propionic acid, ethylbenzene, 4-ethylphenol, and propionamide (used as analogues of the key receptor amino acids) and their mixtures (denoted as S1–S7 biochromatographic models) were used in two developing phases as a model of drug-5-HT receptor interaction. The semiempirical method AM1 (HyperChem v. 7.0 program) and ACD/Labs v. 8.0 program were employed to calculate a set of physicochemical parameters for the investigated compounds. Correlation and multiple linear regression analysis were used to search for the best QSAR equations. The correlations obtained for the compounds studied represent their interactions with the proposed biochromatographic models. The good multivariate relationships (R2 = 0.78–0.84) obtained by means of regression analysis can be used for predicting the quantitative effect of biological activity of different compounds with 5-HT receptor affinity. “Leave-one-out” (LOO) and “leave-N-out” (LNO) cross-validation methods were used to judge the predictive power of final regression equations. PMID:22619602

  7. Applying quantitative structure-activity relationship approaches to nanotoxicology: current status and future potential.

    PubMed

    Winkler, David A; Mombelli, Enrico; Pietroiusti, Antonio; Tran, Lang; Worth, Andrew; Fadeel, Bengt; McCall, Maxine J

    2013-11-01

    The potential (eco)toxicological hazard posed by engineered nanoparticles is a major scientific and societal concern since several industrial sectors (e.g. electronics, biomedicine, and cosmetics) are exploiting the innovative properties of nanostructures resulting in their large-scale production. Many consumer products contain nanomaterials and, given their complex life-cycle, it is essential to anticipate their (eco)toxicological properties in a fast and inexpensive way in order to mitigate adverse effects on human health and the environment. In this context, the application of the structure-toxicity paradigm to nanomaterials represents a promising approach. Indeed, according to this paradigm, it is possible to predict toxicological effects induced by chemicals on the basis of their structural similarity with chemicals for which toxicological endpoints have been previously measured. These structure-toxicity relationships can be quantitative or qualitative in nature and they can predict toxicological effects directly from the physicochemical properties of the entities (e.g. nanoparticles) of interest. Therefore, this approach can aid in prioritizing resources in toxicological investigations while reducing the ethical and monetary costs that are related to animal testing. The purpose of this review is to provide a summary of recent key advances in the field of QSAR modelling of nanomaterial toxicity, to identify the major gaps in research required to accelerate the use of quantitative structure-activity relationship (QSAR) methods, and to provide a roadmap for future research needed to achieve QSAR models useful for regulatory purposes. PMID:23165187

  8. Extraction, separation and quantitative structure-retention relationship modeling of essential oils in three herbs.

    PubMed

    Wei, Yuhui; Xi, Lili; Chen, Dongxia; Wu, Xin'an; Liu, Huanxiang; Yao, Xiaojun

    2010-07-01

    The essential oils extracted from three kinds of herbs were separated by a 5% phenylmethyl silicone (DB-5MS) bonded phase fused-silica capillary column and identified by MS. Seventy-four of the compounds identified were selected as origin data, and their chemical structure and gas chromatographic retention times (RT) were performed to build a quantitative structure-retention relationship model by genetic algorithm and multiple linear regressions analysis. The predictive ability of the model was verified by internal validation (leave-one-out, fivefold, cross-validation and Y-scrambling). As for external validation, the model was also applied to predict the gas chromatographic RT of the 14 volatile compounds not used for model development from essential oil of Radix angelicae sinensis. The applicability domain was checked by the leverage approach to verify prediction reliability. The results obtained using several validations indicated that the best quantitative structure-retention relationship model was robust and satisfactory, could provide a feasible and effective tool for predicting the gas chromatographic RT of volatile compounds and could be also applied to help in identifying the compound with the same gas chromatographic RT. PMID:20506431

  9. Quantitative characterization of processing-microstructure-properties relationships in pressure die-cast magnesium alloys

    NASA Astrophysics Data System (ADS)

    Lee, Soon Gi

    The central goal of this research is to quantitatively characterize the relationships between processing, microstructure, and mechanical properties of important high-pressure die-cast (HPDC) Mg-alloys. For this purpose, a new digital image processing technique for automatic detection and segmentation of gas and shrinkage pores in the cast microstructure is developed and it is applied to quantitatively characterize the effects of HPDC process parameters on the size distribution and spatial arrangement of porosity. To get better insights into detailed geometry and distribution of porosity and other microstructural features, an efficient and unbiased montage based serial sectioning technique is applied for reconstruction of three-dimensional microstructures. The quantitative microstructural data have been correlated to the HPDC process parameters and the mechanical properties. The analysis has led to hypothesis of formation of new type of shrinkage porosity called, "gas induced shrinkage porosity" that has been substantiated via simple heat transfer simulations. The presence of inverse surface macrosegregation has been also shown for the first time in the HPDC Mg-alloys. An image analysis based technique has been proposed for simulations of realistic virtual microstructures that have realistic complex pore morphologies. These virtual microstructures can be implemented in the object oriented finite elements framework to model the variability in the fracture sensitive mechanical properties of the HPDC alloys.

  10. Parametric modeling for quantitative analysis of pulmonary structure to function relationships

    NASA Astrophysics Data System (ADS)

    Haider, Clifton R.; Bartholmai, Brian J.; Holmes, David R., III; Camp, Jon J.; Robb, Richard A.

    2005-04-01

    While lung anatomy is well understood, pulmonary structure-to-function relationships such as the complex elastic deformation of the lung during respiration are less well documented. Current methods for studying lung anatomy include conventional chest radiography, high-resolution computed tomography (CT scan) and magnetic resonance imaging with polarized gases (MRI scan). Pulmonary physiology can be studied using spirometry or V/Q nuclear medicine tests (V/Q scan). V/Q scanning and MRI scans may demonstrate global and regional function. However, each of these individual imaging methods lacks the ability to provide high-resolution anatomic detail, associated pulmonary mechanics and functional variability of the entire respiratory cycle. Specifically, spirometry provides only a one-dimensional gross estimate of pulmonary function, and V/Q scans have poor spatial resolution, reducing its potential for regional assessment of structure-to-function relationships. We have developed a method which utilizes standard clinical CT scanning to provide data for computation of dynamic anatomic parametric models of the lung during respiration which correlates high-resolution anatomy to underlying physiology. The lungs are segmented from both inspiration and expiration three-dimensional (3D) data sets and transformed into a geometric description of the surface of the lung. Parametric mapping of lung surface deformation then provides a visual and quantitative description of the mechanical properties of the lung. Any alteration in lung mechanics is manifest by alterations in normal deformation of the lung wall. The method produces a high-resolution anatomic and functional composite picture from sparse temporal-spatial methods which quantitatively illustrates detailed anatomic structure to pulmonary function relationships impossible for translational methods to provide.

  11. HUBBLE SPACE TELESCOPE ACS IMAGING OF THE GOALS SAMPLE: QUANTITATIVE STRUCTURAL PROPERTIES OF NEARBY LUMINOUS INFRARED GALAXIES WITH L{sub IR} > 10{sup 11.4} L{sub Sun}

    SciTech Connect

    Kim, D.-C.; Evans, A. S.; Privon, G. C. E-mail: aevans@virginia.edu; and others

    2013-05-10

    A Hubble Space Telescope/Advanced Camera for Surveys study of the structural properties of 85 luminous and ultraluminous (L{sub IR} > 10{sup 11.4} L{sub Sun }) infrared galaxies (LIRGs and ULIRGs) in the Great Observatories All-sky LIRG Survey (GOALS) sample is presented. Two-dimensional GALFIT analysis has been performed on F814W ''I-band'' images to decompose each galaxy, as appropriate, into bulge, disk, central point-spread function (PSF) and stellar bar components. The fraction of bulge-less disk systems is observed to be higher in LIRGs (35%) than in ULIRGs (20%), with the disk+bulge systems making up the dominant fraction of both LIRGs (55%) and ULIRGs (45%). Further, bulge+disk systems are the dominant late-stage merger galaxy type and are the dominant type for LIRGs and ULIRGs at almost every stage of galaxy-galaxy nuclear separation. The mean I-band host absolute magnitude of the GOALS galaxies is -22.64 {+-} 0.62 mag (1.8{sup +1.4}{sub -0.4} L{sup *}{sub I}), and the mean bulge absolute magnitude in GOALS galaxies is about 1.1 mag fainter than the mean host magnitude. Almost all ULIRGs have bulge magnitudes at the high end (-20.6 to -23.5 mag) of the GOALS bulge magnitude range. Mass ratios in the GOALS binary systems are consistent with most of the galaxies being the result of major mergers, and an examination of the residual-to-host intensity ratios in GOALS binary systems suggests that smaller companions suffer more tidal distortion than the larger companions. We find approximately twice as many bars in GOALS disk+bulge systems (32.8%) than in pure-disk mergers (15.9%) but most of the disk+bulge systems that contain bars are disk-dominated with small bulges. The bar-to-host intensity ratio, bar half-light radius, and bar ellipticity in GOALS galaxies are similar to those found in nearby spiral galaxies. The fraction of stellar bars decreases toward later merger stages and smaller nuclear separations, indicating that bars are destroyed as the merger

  12. A quantitative assessment of the relationship between precipitation deficits and air temperature variations

    NASA Astrophysics Data System (ADS)

    He, B.; Wang, H. L.; Wang, Q. F.; Di, Z. H.

    2015-06-01

    Previous studies have reported precipitation deficits related to temperature extremes. However, how and to what extent precipitation deficits affect surface air temperatures is still poorly understood. In this study, the relationship between precipitation deficits and surface temperatures was examined in China from 1960 to 2012 based on monthly temperature and precipitation records from 565 stations. Significant negative correlations were identified in each season, with the strongest relationships in the summer, indicating that higher temperatures usually accompanied water-deficient conditions and lower temperatures usually accompanied wet conditions. The examination of the correlations based on 30 year moving windows suggested that the interaction between the two variables has declined over the past three decades. Further investigation indicated a higher impact of extreme dry conditions on temperature than that of extreme wet conditions. In addition, a new simple index (Dry Temperature Index, DTI) was developed and used to quantitatively describe the relationship between water deficits and air temperature variations. We tested and compared the DTI in the coldest month (January) and the hottest month (July) of the year, station by station. In both months, the number of stations with a DThighI ≥ 50% was greater than those with a DThighI < 50%, indicating that a greater proportion of higher temperatures occurred during dry conditions. Based on the results, we conclude that water deficits in China are usually correlated to high temperatures but not to low temperatures.

  13. Quantitative structure-activity relationship correlation between molecular structure and the Rayleigh enantiomeric enrichment factor.

    PubMed

    Jammer, S; Rizkov, D; Gelman, F; Lev, O

    2015-08-01

    It was recently demonstrated that under environmentally relevant conditions the Rayleigh equation is valid to describe the enantiomeric enrichment - conversion relationship, yielding a proportional constant called the enantiomeric enrichment factor, εER. In the present study we demonstrate a quantitative structure-activity relationship model (QSAR) that describes well the dependence of εER on molecular structure. The enantiomeric enrichment factor can be predicted by the linear Hansch model, which correlates biological activity with physicochemical properties. Enantioselective hydrolysis of sixteen derivatives of 2-(phenoxy)propionate (PPMs) have been analyzed during enzymatic degradation by lipases from Pseudomonas fluorescens (PFL), Pseudomonas cepacia (PCL), and Candida rugosa (CRL). In all cases the QSAR relationships were significant with R(2) values of 0.90-0.93, and showed high predictive abilities with internal and external validations providing QLOO(2) values of 0.85-0.87 and QExt(2) values of 0.8-0.91. Moreover, it is demonstrated that this model enables differentiation between enzymes with different binding site shapes. The enantioselectivity of PFL and PCL was dictated by electronic properties, whereas the enantioselectivity of CRL was determined by lipophilicity and steric factors. The predictive ability of the QSAR model demonstrated in the present study may serve as a helpful tool in environmental studies, assisting in source tracking of unstudied chiral compounds belonging to a well-studied homologous series. PMID:26153539

  14. Quantitative relationships between watershed-scale stressors and estuarine condition for mid-Atlantic region

    SciTech Connect

    Paul, J.F.; Hale, S.S.; Comeleo, R.L.; Copeland, J.; August, P.V.

    1995-12-31

    A pilot project has been conducted that developed quantitative relationships between watershed-scale (landscape) stressors and sediment contamination for sub-estuaries within Chesapeake Bay. The landscape stressors, land use patterns (derived from classified, contemporary satellite imagery) and point source pollution, were spatially analyzed for each individual watershed of 25 sub-estuaries using a geographic information system. Sediment contamination data for the sub-estuaries, available from the Environmental Monitoring and Assessment Program (EMAP), were statistically reduced to one principal component for the metals and organics. Non-parametric statistical techniques were used to develop empirical relationships between sediment contamination and developed land (positive), herbaceous land (negative) and point source loadings (positive). These analyses have been extended to (1) include approximately 80 subestuaries across the mid-Atlantic region for which EMAP data were available, and (2) relate landscape stressors with estuarine condition. The measure of estuarine condition was an index of benthic quality developed by EMAP. The only available land use data set for the entire mid-Atlantic region was from US Geological Survey Land Use Data Analysis database, which is of 1970s vintage. Because of the dramatic differences in spatial area of the sub-estuaries in the mid-Atlantic region, adjustments for differing hydrologic regimes had to be factored into the analysis. Results indicate that it is possible to develop relationships between watershed-scale stressors and estuarine condition across large geographic regions.

  15. Establishing a quantitative functional relationship between capillary pressure, saturation and interfacial area. 1997 annual progress report

    SciTech Connect

    Montemagno, C.D.

    1997-01-01

    'There is a fundamental knowledge gap associated with the in situ remediation of non-aqueous phase pollutants. Currently it is not possible to accurately determine the interfacial surface area of non-aqueous contaminants. As a result it is impossible to (1) accurately establish the health and environmental risk associated with the pollution: (2) precisely quantify and evaluate the potential efficacy of various in situ treatment technologies; and (3) conduct reliable performance assessments of the applied remediation technology during and after the clean-up. The global goal of this investigation is to try to remedy these shortcomings through the development of a formalized functional relationship between interfacial area (a), phase saturation (S) and capillary pressure (P). The development of this relationship will allow the direct determination of the fluid-fluid interfacial area from field measurements. Quantitative knowledge of the surface area of the non-aqueous phase pollutant facilitates accurate predictions of both the rate of dissolution and the contact area available for treatment. In addition. if saturation and capillary pressure measurements are made during the remediation process. both the spatial and temporal effectiveness of the remediation technology can be quantified. This information can then be used to optimize the restoration program. The project objective will be achieved through an integrated and focused research program that is comprised of theoretical computational and experimental efforts. These efforts are organized into a framework of four tasks: (1) improve on newly developed laboratory techniques to quantify and directly measure the functional relationship between phase interfacial area (a), saturation (S) and capillary pressure (P). (2) Develop new computational algorithms in conjunction with laboratory measurements to predict P, S and a. (3) Test existing theory and develop new theory to describe the relationship between P, S and a at

  16. Quantitative structure retention relationship studies for predicting relative retention times of chlorinated phenols on gas chromatography.

    PubMed

    Li, Shi-Yin; Sun, Cheng; Wang, Yu; Xu, Shi-Fen; Yao, Shu-Chun; Wang, Lian-Sheng

    2002-07-01

    A new method of quantitative structure-retention relationship (QSRR) studies was reported for predicting gas chromatography (GC) relative retention times (RRTs) of chlorinated phenols (CPs) using a DB-5 column. Chemical descriptors were calculated from the molecular structure of CPs and related to their gas chromatographic RRTs by using multiple linear regression analysis. The proposed model had a multiple square correlation coefficient R2 = 0.970, standard error SE = 0.0472, and significant level P = 0.0000. The QSRR model also reveals that the gas chromatographic relative retention times of CPs are associated with physicochemical property interactions with the stationary phase, and influenced by the number of chlorine and oxygen in the CP mOlecules. PMID:12211996

  17. Quantitative structure-activity relationship of antifungal activity of rosin derivatives.

    PubMed

    Wang, Hui; Nguyen, Thi Thanh Hien; Li, Shujun; Liang, Tao; Zhang, Yuanyuan; Li, Jian

    2015-01-15

    To develop new rosin-based wood preservatives with good antifungal activity, 24 rosin derivatives were synthesized, bioassay tested with Trametes versicolor and Gloeophyllum trabeum, and subjected to analysis of their quantitative structure-activity relationships (QSAR). A QSAR analysis using Ampac 9.2.1 and Codessa 2.7.16 software built two QSAR models of antifungal ratio for T. versicolor and G. trabeum with values of R(2)=0.9740 and 0.9692, respectively. Based on the models, tri-N-(3-hydroabietoxy-2-hydroxy) propyl-triethyl ammonium chloride was designed and the bioassay test result proved its better inhibitory effect against the two selected fungi as expected. PMID:25466709

  18. A quantitative structure-activity relationship approach for assessing toxicity of mixture of organic compounds.

    PubMed

    Chang, C M; Ou, Y H; Liu, T-C; Lu, S-Y; Wang, M-K

    2016-06-01

    Four types of reactivity indices were employed to construct quantitative structure-activity relationships for the assessment of toxicity of organic chemical mixtures. Results of analysis indicated that the maximum positive charge of the hydrogen atom and the inverse of the apolar surface area are the most important descriptors for the toxicity of mixture of benzene and its derivatives to Vibrio fischeri. The toxicity of mixture of aromatic compounds to green alga Scenedesmus obliquus is mainly affected by the electron flow and electrostatic interactions. The electron-acceptance chemical potential and the maximum positive charge of the hydrogen atom are found to be the most important descriptors for the joint toxicity of aromatic compounds. PMID:27426856

  19. Quantitative relationship between mutagenicity and structure of heterocyclic analogs of pyrene and phenanthrene

    SciTech Connect

    Baskin, I.I.; Lyubimova, I.K.; Abilev, S.K.

    1994-12-31

    In this work, the authors investigated quantitative relationships between mutagenicity and chemical structures of certain heterocyclic analogs of pyrene and phenanthrene that have yet to be examined. Compounds were synthesized using the methods described earlier. The compounds were tested for mutagenic activity by Ames` method. They used the strain Salmonella typhimurium TA1538 (his D3052, rfa, uvr), which registered the reading frame shift mutations. Analysis of the data suggests that the most considerable increases in mutagenicity occur with two nitro groups at positions 2 and 7. When nitro groups occur at other positions, the molecule displayed no mutagenicity, irrespective of the number of groups. Two amino groups at the same position, one amino and one carboxyl group, or chlorine atoms impart a weaker mutagenicity to the molecule. The mutagenic properties were lost on shifting the amino groups from positions 2,7 to 1,6.

  20. Quantitative structure-activity relationships of selective antagonists of glucagon receptor using QuaSAR descriptors.

    PubMed

    Manoj Kumar, Palanivelu; Karthikeyan, Chandrabose; Hari Narayana Moorthy, Narayana Subbiah; Trivedi, Piyush

    2006-11-01

    In the present paper, quantitative structure activity relationship (QSAR) approach was applied to understand the affinity and selectivity of a novel series of triaryl imidazole derivatives towards glucagon receptor. Statistically significant and highly predictive QSARs were derived for glucagon receptor inhibition by triaryl imidazoles using QuaSAR descriptors of molecular operating environment (MOE) employing computer-assisted multiple regression procedure. The generated QSAR models revealed that factors related to hydrophobicity, molecular shape and geometry predominantly influences glucagon receptor binding affinity of the triaryl imidazoles indicating the relevance of shape specific steric interactions between the molecule and the receptor. Further, QSAR models formulated for selective inhibition of glucagon receptor over p38 mitogen activated protein (MAP) kinase of the compounds in the series highlights that the same structural features, which influence the glucagon receptor affinity, also contribute to their selective inhibition. PMID:17077558

  1. Development of quantitative structure activity relationships for the binding affinity of methoxypyridinium cations for human acetylcholinesterase.

    PubMed

    Morrill, Jason A; Topczewski, Joseph J; Lodge, Alexander M; Yasapala, Nilanthi; Quinn, Daniel M

    2015-11-01

    Among the most toxic substances known are the organophosphorus (OP) compounds used as pesticides and chemical warfare agents. Owing to their high toxicity there is a number of efforts underway to develop effective therapies for OP agent exposure. To date all therapies in use treat inhibited acetylcholinesterase (AChE), but are ineffective for the treatment of inhibited AChE, which has undergone a subsequent hydrolysis process, referred to as aging. Toward developing a therapy for treating victims of OP intoxication in the aged state we have developed Quantitative Structure-Activity Relationships (QSARs) based on the AM1 semiempirical quantum mechanical method using the program, CODESSA (COmprehensive Descriptors for Structural and Statistical Analysis). Using this methodology we obtained a multiple correlation QSAR equation which gave R(2)=0.9359 for a random training set of 38 ligands and R(2)=0.9236 for prediction on a random test set of 9 ligands. PMID:26454505

  2. Quantitative structure-retention relationships of cannabimimetic aminoalkilindole derivatives and their metabolites.

    PubMed

    D'Archivio, Angelo Antonio; Maggi, Maria Anna; Ruggieri, Fabrizio

    2015-05-10

    Development of chromatographic analyses of synthetic cannabinoids is complicated by the lack of commercial reference standards, especially for new analogues introduced in the clandestine market to bypass legal controls and for their metabolites. In the present work, we explore the possibility of predicting the retention behaviour of the cannabimimetic aminoalkilindoles and their urinary metabolites in high-performance liquid-chromatography using a quantitative structure-retention relationship (QSRR) generated by multilinear regression. To represent the structure of the 43 investigated analytes, 617 computational molecular descriptors are subjected to genetic algorithm variable selection aimed at identifying a small but informative subset. Predictive performance of the QSRR model is evaluated on an external set consisting of 10 representative compounds, including both drugs and their metabolites, and, successively by a Monte Carlo validation method. The best QSRR model, based on six molecular descriptors, exhibits a promising predictive performance and robustness. PMID:25767909

  3. Quantitative structure-activity relationships for cellular uptake of surface-modified nanoparticles.

    PubMed

    Liu, Rong; Rallo, Robert; Bilal, Muhammad; Cohen, Yoram

    2015-01-01

    Quantitative structure-activity relationships (QSARs) were developed, for cellular uptake of nanoparticles (NPs) of the same iron oxide core but with different surface-modifying organic molecules, based on linear and non-linear (epsilon support vector regression (ε-SVR)). A linear QSAR provided high prediction accuracy of R2=0.751 (coefficient of determination) using 11 descriptors selected from an initial pool of 184 descriptors calculated for the NP surfacemodifying molecules, while a ε-SVR based QSAR with only 6 descriptors improved prediction accuracy to R2=0.806. The linear and ε-SVR based QSARs both demonstrated good robustness and well spanned applicability domains. It is suggested that the approach of evaluating pertinent descriptors and their significance, via QSAR analysis, to cellular NP uptake could support planning and interpretation of toxicity studies as well as provide guidance for the tailor-design NPs with respect to targeted cellular uptake for various applications. PMID:25747434

  4. Quantitative Structure-Cytotoxic Activity Relationship 1-(Benzoyloxy)urea and Its Derivative.

    PubMed

    Hardjono, Suko; Siswodihardjo, Siswandono; Pramono, Purwanto; Darmanto, Win

    2016-01-01

    Drug development is originally carried out on a trial and error basis and it is cost-prohibitive. To minimize the trial and error risks, drug design is needed. One of the compound development processes to get a new drug is by designing a structure modification of the mother compound whose activities are recognized. A substitution of the mother compounds alters the physicochemical properties: lipophilic, electronic and steric properties. In Indonesia, one of medical treatments to cure cancer is through chemotherapy and hydroxyurea. Some derivatives, phenylthiourea, phenylurea, benzoylurea, thiourea and benzoylphenylurea, have been found to be anticancer drug candidates. To predict the activity of the drug compound before it is synthesized, the in-silico test is required. From the test, Rerank Score which is the energy of interaction between the receptor and the ligand molecule is then obtained. Hydroxyurea derivatives were synthesized by modifying Schotten-Baumann's method by the addition of benzoyl group and its homologs resulted in the increase of lipophilic, electronic and steric properties, and cytotoxic activity. Synthesized compounds were 1-(benzoyloxy)urea and its derivatives. Structure characterization was obtained by the spectrum of UV, IR, H NMR, C NMR and Mass Spectrometer. Anticancer activity was carried out using MTT method on HeLa cells. The Quantitative Structure-Cytotoxic Activity Relationships of 1-(benzoyloxy)urea compound and its derivatives was calculated using SPSS. The chemical structure was described, namely: ClogP, π, σ, RS, CMR and Es; while, the cytotoxic activity was indicated by log (1 / IC50). The results show that the best equation of Quantitative Structure-Cytotoxic Activity Relationships (QSAR) of 1- (benzoyloxy)urea compound and its derivatives is Log 1/IC50 = - 0.205 (+ 0.068) σ - 0.051 (+ 0.022) Es - 1.911 (+ 0.020). PMID:27222144

  5. Quantitative Relationships between Photosynthetic, Nitrogen Fixing, and Fermentative H2 Metabolism in a Photosynthetic Microbial Mat

    NASA Technical Reports Server (NTRS)

    Hoehler, Tori M.; Albert, Daniel B.; Bebout, Brad M.; Turk, Kendra A.; DesMarais, David J.

    2004-01-01

    The ultimate potential of any microbial ecosystem to contribute chemically to its environment - and therefore, to impact planetary biogeochemistry or to generate recognizable biosignatures - depends not only on the individual metabolic capabilities of constituent organisms, but also on how those capabilities are expressed through interactions with neighboring organisms. This is particularly important for microbial mats, which compress an extremely broad range of metabolic potential into a small and dynamic system. H2 participates in many of these metabolic processes, including the major elemental cycling processes of photosynthesis, nitrogen fixation, sulfate reduction, and fermentation, and may therefore serve as a mediator of microbial interactions within the mat system. Collectively, the requirements of energy, electron transfer, and biomass element stoichiometry suggest quantitative relationships among the major element cycling processes, as regards H2 metabolism We determined experimentally the major contributions to 32 cycling in hypersaline microbial mats from Baja California, Mexico, and compared them to predicted relationships. Fermentation under dark, anoxic conditions is quantitatively the most important mechanism of H2 production, consistent with expectations for non-heterocystous mats such as those under study. Up to 16% of reducing equivalents fixed by photosynthesis during the day may be released by this mechanism. The direct contribution of nitrogen fixation to H2 production is small in comparison, but this process may indirectly stimulate substantial H2 generation, by requiring higher rates of fermentation. Sulfate reduction, aerobic consumption, diffusive and ebulitive loss, and possibly H2-based photoreduction of CO2 serve as the principal H2 sinks. Collectively, these processes interact to create an orders-of-magnitude daily variation in H2 concentrations and fluxes, and thereby in the oxidation-reduction potential that is imposed on microbial

  6. Relationship of Q-Sweat to Quantitative Sudomotor Axon Reflex Test (QSART) Volumes

    PubMed Central

    Sletten, David M.; Weigand, Stephen D.; Low, Phillip A.

    2009-01-01

    Q-Sweat, a commercial quantitative sweat measurement system, is modeled on Quantitative Sudomotor Axon Reflex Testing (QSART). The current study investigated the sweat response using Q-Sweat and Mayo-QSART recordings under identical conditions in healthy normal controls. Ninety-four participants were recruited for this study. All participants underwent randomized bilateral QSART recordings over the four standard recording regions. For both men and women, Wilcoxon signed rank tests of paired differences showed significantly lower volumes at each of the four sites for Q-Sweat vs. Mayo-QSART. Linear regression analysis was used to estimate the relationship between Q-Sweat and Mayo-QSART volume measurements separately for men and women. Although there was variability about the regression lines, these fitted models can be used to estimate the expected Mayo-QSART volume given an observed Q-Sweat volume, although it is preferable to use the Q-Sweat normative database directly. We hypothesize that the constant current generator used in conjunction with Q-Sweat provides a less efficient iontophoresis of acetylcholine than the Mayo-constructed constant current stimulator and results in lower volumes. PMID:19768767

  7. The Relationship between Gray Matter Quantitative MRI and Disability in Secondary Progressive Multiple Sclerosis

    PubMed Central

    Gracien, René-Maxime; Jurcoane, Alina; Wagner, Marlies; Reitz, Sarah C.; Mayer, Christoph; Volz, Steffen; Hof, Stephanie-Michelle; Fleischer, Vinzenz; Droby, Amgad; Steinmetz, Helmuth; Zipp, Frauke; Hattingen, Elke; Deichmann, Ralf; Klein, Johannes C.

    2016-01-01

    Purpose In secondary progressive Multiple Sclerosis (SPMS), global neurodegeneration as a driver of disability gains importance in comparison to focal inflammatory processes. However, clinical MRI does not visualize changes of tissue composition outside MS lesions. This quantitative MRI (qMRI) study investigated cortical and deep gray matter (GM) proton density (PD) values and T1 relaxation times to explore their potential to assess neuronal damage and its relationship to clinical disability in SPMS. Materials and Methods 11 SPMS patients underwent quantitative T1 and PD mapping. Parameter values across the cerebral cortex and deep GM structures were compared with 11 healthy controls, and correlation with disability was investigated for regions exhibiting significant group differences. Results PD was increased in the whole GM, cerebral cortex, thalamus, putamen and pallidum. PD correlated with disability in the whole GM, cerebral cortex, putamen and pallidum. T1 relaxation time was prolonged and correlated with disability in the whole GM and cerebral cortex. Conclusion Our study suggests that the qMRI parameters GM PD (which likely indicates replacement of neural tissue with water) and cortical T1 (which reflects cortical damage including and beyond increased water content) are promising qMRI candidates for the assessment of disease status, and are related to disability in SPMS. PMID:27513853

  8. Synthesis, biological activities, and quantitative structure-activity relationship (QSAR) study of novel camptothecin analogues.

    PubMed

    Wu, Dan; Zhang, Shao-Yong; Liu, Ying-Qian; Wu, Xiao-Bing; Zhu, Gao-Xiang; Zhang, Yan; Wei, Wei; Liu, Huan-Xiang; Chen, An-Liang

    2015-01-01

    In continuation of our program aimed at the development of natural product-based pesticidal agents, three series of novel camptothecin derivatives were designed, synthesized, and evaluated for their biological activities against T. Cinnabarinus, B. brassicae, and B. xylophilus. All of the derivatives showed good-to-excellent activity against three insect species tested, with LC50 values ranging from 0.00761 to 0.35496 mmol/L. Remarkably, all of the compounds were more potent than CPT against T. Cinnabarinus, and compounds 4d and 4c displayed superior activity (LC50 0.00761 mmol/L and 0.00942 mmol/L, respectively) compared with CPT (LC50 0.19719 mmol/L) against T. Cinnabarinus. Based on the observed bioactivities, preliminary structure-activity relationship (SAR) correlations were also discussed. Furthermore, a three-dimensional quantitative structure-activity relationship (3D-QSAR) model using comparative molecular field analysis (CoMFA) was built. The model gave statistically significant results with the cross-validated q2 values of 0.580 and correlation coefficient r2 of 0.991 and  of 0.993. The QSAR analysis indicated that the size of the substituents play an important in the activity of 7-modified camptothecin derivatives. These findings will pave the way for further design, structural optimization, and development of camptothecin-derived compounds as pesticidal agents. PMID:25985362

  9. Quantitative structure-retention relationship of selected imidazoline derivatives on α1-acid glycoprotein column.

    PubMed

    Filipic, Slavica; Ruzic, Dusan; Vucicevic, Jelica; Nikolic, Katarina; Agbaba, Danica

    2016-08-01

    The retention behaviour of 22 selected imidazoline drugs and derivatives was investigated on α1-acid glycoprotein (AGP) column using Sørensen phosphate buffer (pH 7.0) and 2-propanol as organic modifier. Quantitative Structure-Retention Relationships (QSRR) models were built using extrapolated logkw values as well as isocratic retention factors (logk5, logk8, logk10, logk12, logk15 obtained for 5%, 8%, 10%, 12%, and 15%, of 2-propanol in mobile phase, respectively) as dependant variables and calculated physicochemical parameters as independant variables. The established QSRR models were built by stepwise multiple linear regression (MLR) and partial least squares regression (PLS). The performance of the stepwise and PLS models was tested by cross-validation and the external test set prediction. The validated QSRR models were compared and the optimal PLS-QSRR model for logkw and each isocratic retention factors (PLS-QSRR(logk5), PLS-QSRR(logk8), PLS-QSRR(logk10), MLR-QSRR(logk12), MLR-QSRR(logk15)) were selected. The QSRR results were further confirmed by Linear Solvation Energy Relationships (LSER). LSER analysis indicated on hydrogen bond basicity, McGowan volume and excess molar refraction as the most significant parameters for all AGP chromatographic retention factors and logkw values of 22 selected imidazoline drugs and derivatives. PMID:26968888

  10. Quantitative causal-comparative relationship between interactive whiteboard instruction and student science proficiency

    NASA Astrophysics Data System (ADS)

    Danelczyk, Ewa Krystyna

    The purpose of this quantitative causal-comparative study was to investigate the relationship between the instructional effects of the interactive whiteboard and students' proficiency levels in eighth-grade science as evidenced by the state FCAT scores. A total of 46 eighth-grade science teachers in a South Florida public school district completed a survey via the Internet. Data were analyzed using descriptive statistics, t tests, Pearson's product moment correlation, and Spearman's rank order correlation. Results revealed a significant difference in mean between eighth-grade students' proficiency percentages reported by participating teachers and the statewide results for the years 2008-2012 (p < .0005), with the exception of results reported in the year 2010 (p > .05). The significant results were not found between use of the interactive whiteboard for science instruction and students' science proficiency levels as evidenced by FCAT (p > .05), and teachers' professional experience and students' proficiency levels (p > .05). The recommendation from the current study is to continue research pertaining to instructional effectiveness of the interactive whiteboard in relationship to standardized tests because existing findings on similar topics are contradictory. There is a need for more empirical evidence on the long-term impact of the interactive whiteboard on students' achievement in science.

  11. Quantitative structure-chromatographic retention relationship for polycyclic aromatic sulfur heterocycles.

    PubMed

    Xu, Hui-Ying; Zou, Jian-Wei; Jiang, Yong-Jun; Hu, Gui-Xiang; Yu, Qing-Sen

    2008-07-11

    Polycyclic aromatic sulfur heterocycles (PASHs) are of concern in petroleum geochemistry and environmental chemistry. In the present study, geometrical optimization and electrostatic potential calculations have been performed for 114 PASHs reported previously at the HF/6-31G* level of theory. A group of 25 statistically based parameters have been extracted. Linear relationships between gas-chromatographic retention index (RI) and the structural descriptors have been established by stepwise linear regression analysis. The result shows that two quantities derived from positive electrostatic potential on molecular surface, V(s)(+) (the average value of the positive electrostatic potentials on molecular surface) and sigma(+)(2) (a measure of dispersion tendency of positive electrostatic potential), together with V(mc) (the molecular volume) and E(HOMO) (the energy of the highest occupied molecular orbital) can be well used to express the quantitative structure-retention relationship (QSRR) of PASHs. Predictive capability of the model has been demonstrated by leave-one-out cross-validation with the cross-validated correlation coefficient (R(CV)) of 0.992. Furthermore, when splitting the 114 PASH samples into calibration and test sets in the ratio of 2:1, a similar treatment yields an equation of almost equal statistical quality and very similar regression coefficients, validating the robustness of our model. Predictions for six PASHs from other source have also been made. The QSRR model established may provide a new powerful method for predicting chromatographic properties of aromatic organosulfur compounds. PMID:18534609

  12. A quantitative structure-activity relationship model for radical scavenging activity of flavonoids.

    PubMed

    Om, A; Kim, J H

    2008-03-01

    A quantitative structure-activity relationship (QSAR) study has been carried out for a training set of 29 flavonoids to correlate and predict the 1,1-diphenyl-2-picrylhydrazyl radical scavenging activity (RSA) values obtained from published data. Genetic algorithm and multiple linear regression were employed to select the descriptors and to generate the best prediction model that relates the structural features to the RSA activities using (1) three-dimensional (3D) Dragon (TALETE srl, Milan, Italy) descriptors and (2) semi-empirical descriptor calculations. The predictivity of the models was estimated by cross-validation with the leave-one-out method. The result showed that a significant improvement of the statistical indices was obtained by deleting outliers. Based on the data for the compounds used in this study, our results suggest a QSAR model of RSA that is based on the following descriptors: 3D-Morse, WHIM, and GETAWAY. Therefore, satisfactory relationships between RSA and the semi-empirical descriptors were found, demonstrating that the energy of the highest occupied molecular orbital, total energy, and energy of heat of formation contributed more significantly than all other descriptors. PMID:18361735

  13. HomoSAR: bridging comparative protein modeling with quantitative structural activity relationship to design new peptides.

    PubMed

    Borkar, Mahesh R; Pissurlenkar, Raghuvir R S; Coutinho, Evans C

    2013-11-15

    Peptides play significant roles in the biological world. To optimize activity for a specific therapeutic target, peptide library synthesis is inevitable; which is a time consuming and expensive. Computational approaches provide a promising way to simply elucidate the structural basis in the design of new peptides. Earlier, we proposed a novel methodology termed HomoSAR to gain insight into the structure activity relationships underlying peptides. Based on an integrated approach, HomoSAR uses the principles of homology modeling in conjunction with the quantitative structural activity relationship formalism to predict and design new peptide sequences with the optimum activity. In the present study, we establish that the HomoSAR methodology can be universally applied to all classes of peptides irrespective of sequence length by studying HomoSAR on three peptide datasets viz., angiotensin-converting enzyme inhibitory peptides, CAMEL-s antibiotic peptides, and hAmphiphysin-1 SH3 domain binding peptides, using a set of descriptors related to the hydrophobic, steric, and electronic properties of the 20 natural amino acids. Models generated for all three datasets have statistically significant correlation coefficients (r(2)) and predictive r2 (r(pred)2) and cross validated coefficient ( q(LOO)2). The daintiness of this technique lies in its simplicity and ability to extract all the information contained in the peptides to elucidate the underlying structure activity relationships. The difficulties of correlating both sequence diversity and variation in length of the peptides with their biological activity can be addressed. The study has been able to identify the preferred or detrimental nature of amino acids at specific positions in the peptide sequences. PMID:24105965

  14. Quantitative residue-level structure-evolution relationships in the yeast membrane proteome.

    PubMed

    Franzosa, Eric A; Xue, Ran; Xia, Yu

    2013-01-01

    Membrane proteins exist in distinctly different environments than do soluble proteins, resulting in differences between their respective biophysical and evolutionary properties. In comparison with soluble proteins, relatively little is known about how the unique biophysical properties of membrane proteins affect their evolutionary properties at the residue level. In particular, transmembrane (TM) regions of membrane proteins tend to be more conserved than regions outside of the membrane (extramembrane [EM] regions), but the mechanisms underlying this phenomenon are not well understood. Here, we combine homology-based high-resolution three-dimensional protein models with rigorous evolutionary rate calculations to quantitatively assess residue-level structure-evolution relationships in the yeast membrane proteome. We find that residue evolutionary rate increases linearly with decreasing residue burial, regardless of the hydrophobic or hydrophilic nature of the solvent environment. This finding supports a direct relationship between a residue's selective constraint and the extent of its packing interactions with neighboring residues, independent of hydrophobic effects. Most importantly, for a fixed degree of burial, residues from TM regions tend to evolve more slowly than residues from EM regions. We attribute this difference to the increased importance of packing constraints and the decreased importance of hydrophobic effects in TM regions. This additional selective constraint on TM residues plays a dominant role in explaining why TM regions evolve more slowly than EM regions. In addition to revealing the universality of the linear relationship between residue burial and selective constraint across solvent environments, our work highlights the distinct residue-level evolutionary consequences imposed by the unique biophysical properties of the membrane environment. PMID:23512408

  15. Ecomorphology of morpho-functional relationships in the family of Sparidae: a quantitative statistic approach.

    PubMed

    Antonucci, Francesca; Costa, Corrado; Aguzzi, Jacopo; Cataudella, Stefano

    2009-07-01

    In many fish species, morphological similarity can be considered as a proxy for similarities in habitat use. The Sparidae family includes species that are recognized for common morphological features such as structure and positioning of the fins and specialized dentition. The aim of this study was to quantitatively describe the relationship of body shape morphology with habitat use, trophic level, and systematics in the majority of known Sparidae species (N = 92). This ecomorphological comparison was performed with a geometric morphometric approach considering as variables the Trophic Index (TROPH), the habitat (i.e., classified as demersal, benthopelagic and reef associated) and the phylogenetic relationship of species at the subfamily level. The analysis by the TROPH variable showed a positive relation with shape because the morphological features of all the species are strongly correlated with their trophic behavior (e.g., herbivore species have a smaller mouth gap that make them able to feed upon sessile resources). The morphological analysis according to the Habitat variable was used to classify species according to a feeding-habitat niche in terms of portion of the water column and seabed space where species mostly perform their behavioral activities. We described three kinds of morphological designs in relation to a benthopelagic, demersal and reef-associated habit. The six subfamily groups were morphologically well distinguishable and the cladogram relative to Mahalanobis' morphological distances was compared with those proposed by other authors. We also quantified the phylogenetic relationship among the different subfamilies based on the analysis of shape in relation to trophic ecology, confirming the observations of the authors. PMID:19180528

  16. Quantitative Structure Activity Relationship for Inhibition of Human Organic Cation/Carnitine Transporter (OCTN2)

    PubMed Central

    Diao, Lei; Ekins, Sean; Polli, James E.

    2010-01-01

    Organic cation/carnitine transporter (OCTN2; SLC22A5) is an important transporter for L-carnitine homeostasis, but can be inhibited by drugs, which may cause L-carnitine deficiency and possibly other OCTN2-mediated drug-drug interactions. One objective was to develop a quantitative structure–activity relationship (QSAR) of OCTN2 inhibitors, in order to predict and identify other potential OCTN2 inhibitors and infer potential clinical interactions. A second objective was to assess two high renal clearance drugs that interact with OCTN2 in vitro (cetirizine and cephaloridine) for possible OCTN2-mediated drug-drug interactions. Using previously generated in vitro data of 22 drugs, a 3D quantitative pharmacophore model and a Bayesian machine learning model were developed. The four pharmacophore features include two hydrophobic groups, one hydrogen-bond acceptor, and one positive ionizable center. The Bayesian machine learning model was developed using simple interpretable descriptors and function class fingerprints of maximum diameter 6 (FCFP_6). An external test set of 27 molecules, including 15 newly identified OCTN2 inhibitors, and a literature test set of 22 molecules were used to validate both models. The computational models afforded good capability to identify structurally diverse OCTN2 inhibitors, providing a valuable tool to predict new inhibitors efficiently. Inhibition results confirmed our previously observed association between rhabdomyolysis and Cmax/Ki ratio. The two high renal clearance drugs cetirizine and cephaloridine were found not to be OCTN2 substrates and their diminished elimination by other drugs is concluded not to be mediated by OCTN2. PMID:20831193

  17. Genetic programming based quantitative structure-retention relationships for the prediction of Kovats retention indices.

    PubMed

    Goel, Purva; Bapat, Sanket; Vyas, Renu; Tambe, Amruta; Tambe, Sanjeev S

    2015-11-13

    The development of quantitative structure-retention relationships (QSRR) aims at constructing an appropriate linear/nonlinear model for the prediction of the retention behavior (such as Kovats retention index) of a solute on a chromatographic column. Commonly, multi-linear regression and artificial neural networks are used in the QSRR development in the gas chromatography (GC). In this study, an artificial intelligence based data-driven modeling formalism, namely genetic programming (GP), has been introduced for the development of quantitative structure based models predicting Kovats retention indices (KRI). The novelty of the GP formalism is that given an example dataset, it searches and optimizes both the form (structure) and the parameters of an appropriate linear/nonlinear data-fitting model. Thus, it is not necessary to pre-specify the form of the data-fitting model in the GP-based modeling. These models are also less complex, simple to understand, and easy to deploy. The effectiveness of GP in constructing QSRRs has been demonstrated by developing models predicting KRIs of light hydrocarbons (case study-I) and adamantane derivatives (case study-II). In each case study, two-, three- and four-descriptor models have been developed using the KRI data available in the literature. The results of these studies clearly indicate that the GP-based models possess an excellent KRI prediction accuracy and generalization capability. Specifically, the best performing four-descriptor models in both the case studies have yielded high (>0.9) values of the coefficient of determination (R(2)) and low values of root mean squared error (RMSE) and mean absolute percent error (MAPE) for training, test and validation set data. The characteristic feature of this study is that it introduces a practical and an effective GP-based method for developing QSRRs in gas chromatography that can be gainfully utilized for developing other types of data-driven models in chromatography science

  18. Quantitative structure-retention relationships of flavonoids unraveled by immobilized artificial membrane chromatography.

    PubMed

    Santoro, Adriana Leandra; Carrilho, Emanuel; Lanças, Fernando Mauro; Montanari, Carlos Alberto

    2016-06-10

    The pharmacokinetic properties of flavonoids with differing degrees of lipophilicity were investigated using immobilized artificial membranes (IAMs) as the stationary phase in high performance liquid chromatography (HPLC). For each flavonoid compound, we investigated whether the type of column used affected the correlation between the retention factors and the calculated octanol/water partition (log Poct). Three-dimensional (3D) molecular descriptors were calculated from the molecular structure of each compound using i) VolSurf software, ii) the GRID method (computational procedure for determining energetically favorable binding sites in molecules of known structure using a probe for calculating the 3D molecular interaction fields, between the probe and the molecule), and iii) the relationship between partition and molecular structure, analyzed in terms of physicochemical descriptors. The VolSurf built-in Caco-2 model was used to estimate compound permeability. The extent to which the datasets obtained from different columns differ both from each other and from both the calculated log Poct and the predicted permeability in Caco-2 cells was examined by principal component analysis (PCA). The immobilized membrane partition coefficients (kIAM) were analyzed using molecular descriptors in partial least square regression (PLS) and a quantitative structure-retention relationship was generated for the chromatographic retention in the cholesterol column. The cholesterol column provided the best correlation with the permeability predicted by the Caco-2 cell model and a good fit model with great prediction power was obtained for its retention data (R(2)=0.96 and Q(2)=0.85 with four latent variables). PMID:26916828

  19. Quantitative structure carcinogenicity relationship for detecting structural alerts in nitroso-compounds

    SciTech Connect

    Helguera, Aliuska Morales Cordeiro, M. Natalia D.S.; Perez, Miguel Angel Cabrera; Combes, Robert D.; Gonzalez, Maykel Perez

    2008-09-01

    In this work, Quantitative Structure-Activity Relationship (QSAR) modelling was used as a tool for predicting the carcinogenic potency of a set of 39 nitroso-compounds, which have been bioassayed in male rats by using the oral route of administration. The optimum QSAR model provided evidence of good fit and performance of predicitivity from training set. It was able to account for about 84% of the variance in the experimental activity and exhibited high values of the determination coefficients of cross validations, leave one out and bootstrapping (q{sup 2}{sub LOO} = 78.53 and q{sup 2}{sub Boot} = 74.97). Such a model was based on spectral moments weighted with Gasteiger-Marsilli atomic charges, polarizability and hydrophobicity, as well as with Abraham indexes, specifically the summation solute hydrogen bond basicity and the combined dipolarity/polarizability. This is the first study to have explored the possibility of combining Abraham solute descriptors with spectral moments. A reasonable interpretation of these molecular descriptors from a toxicological point of view was achieved by means of taking into account bond contributions. The set of relationships so derived revealed the importance of the length of the alkyl chains for determining carcinogenic potential of the chemicals analysed, and were able to explain the difference between mono-substituted and di-substituted nitrosoureas as well as to discriminate between isomeric structures with hydroxyl-alkyl and alkyl substituents in different positions. Moreover, they allowed the recognition of structural alerts in classical structures of two potent nitrosamines, consistent with their biotransformation. These results indicate that this new approach has the potential for improving carcinogenicity predictions based on the identification of structural alerts.

  20. Quantitative structure-activity relationship models for prediction of the toxicity of polybrominated diphenyl ether congeners.

    PubMed

    Wang, Yawei; Liu, Huanxiang; Zhao, Chunyan; Liu, Hanxia; Cai, Zongwei; Jiang, Guibin

    2005-07-01

    Levels of polybrominated diphenyl ethers (PBDEs) are increasing in the environment and may cause long-term health problems in humans. The similarity in the chemical structures of PBDEs and other halogenated aromatic pollutants hints on the possibility that they might share similar toxicological effects. In this work, three-dimensional quantitative structure activity relationships (3-D-QSAR) models, using comparative molecular field analysis (CoMFA) and comparative similarity indices analysis (CoMSIA), were built based on calculated structural indices and a reported experimental toxicology index (aryl hydrocarbon receptor relative binding affinities, RBA) of 18 PBDEs congeners, to determine the factors required for the RBA of these PBDEs. After performing leave-one-out cross-validation, satisfactory results were obtained with cross-validation O2 and R2 values of 0.580 and 0.995 by the CoMFA model and 0.680 and 0.982 by the CoMSIA model, respectively. The results showed clearly that the nonplanar conformations of PBDEs result in the lowest energy level and that the electrostatic index was the main factor reflecting the RBA of PBDEs. The two QSAR models were then used to predict the RBA value of 46 PBDEs for which experimental values are unavailable at present. PMID:16053097

  1. A quantitative structure--activity relationship model for the intrinsic activity of uncouplers of oxidative phosphorylation.

    PubMed

    Spycher, Simon; Escher, Beate I; Gasteiger, Johann

    2005-12-01

    A quantitative structure-activity relationship (QSAR) has been derived for the prediction of the activity of phenols in uncoupling oxidative and photophosphorylation. Twenty-one compounds with experimental data for uncoupling activity as well as for the acid dissociation constant, pKa, and for partitioning constants of the neutral and the charged species into model membranes were analyzed. From these measured data, the effective concentration in the membrane was derived, which allowed the study of the intrinsic activity of uncouplers within the membrane. A linear regression model for the intrinsic activity could be established using the following three descriptors: solvation free energies of the anions, an estimate for heterodimer formation describing transport processes, and pKa values describing the speciation of the phenols. In a next step, the aqueous effect concentrations were modeled by combining the model for the intrinsic uncoupling activity with descriptors accounting for the uptake into membranes. Results obtained with experimental membrane-water partitioning data were compared with the results obtained with experimental octanol-water partition coefficients, log Kow, and with calculated log Kow values. The properties of these different measures of lipophilicity were critically discussed. PMID:16359176

  2. Quantitative structure-activity relationships for weak acid respiratory uncouplers to Vibrio fisheri

    SciTech Connect

    Schultz, T.W.; Cronin, M.T.D.

    1997-02-01

    Acute toxicity values of 16 organic compounds thought to elicit their response via the weak acid respiratory uncoupling mechanism of toxic action were secured from the literature. Regression analysis of toxicities revealed that a measured 5-min V. fisheri potency value can be used as a surrogate for the 30-min value. Regression analysis of toxicity versus hydrophobicity, measured as the 1-octanol/water partition coefficient (log K{sub ow}), was used to formulate a quantitative structure-activity relationship (QSAR). The equation log pT{sub 30}{sup {minus}1} = 0.489(log K{sub ow}) + 0.126 was found to be a highly predictive model. This V. fisheri QSAR is statistically similar to QSARs generated from weak acid uncoupler potency data for Pimephales promelas survivability and Tetrahymena pyriformis population growth impairment. This work, therefore, suggests that the weak acid respiratory uncoupling mechanism of toxic action is present in V. fisheri, and as such is not restricted to mitochondria-containing organisms.

  3. Acute toxicity estimation by calculation--Tubifex assay and quantitative structure-activity relationships.

    PubMed

    Tichý, Milon; Rucki, Marian; Hanzlíková, Iveta; Roth, Zdenek

    2008-11-01

    A quantitative structure-activity relationship (QSAR) model dependent on log P(n - octanol/water), or log P(OW), was developed with acute toxicity index EC50, the median effective concentration measured as inhibition of movement of the oligochaeta Tubifex tubifex with 3 min exposure, EC50(Tt) (mol/L): log EC50(Tt) = -0.809 (+/-0.035) log P(OW) - 0.495 (+/-0.060), n=82, r=0.931, r2=0.867, residual standard deviation of the estimate 0.315. A learning series for the QSAR model with the oligochaete contained alkanols, alkenols, and alkynols; saturated and unsaturated aldehydes; aniline and chlorinated anilines; phenol and chlorinated phenols; and esters. Three cross-validation procedures proved the robustness and stability of QSAR models with respect to the chemical structure of compounds tested within a series of compounds used in the learning series. Predictive ability was described by q2 .801 (cross-validated r2; predicted variation estimated with cross-validation) in LSO (leave-a structurally series-out) cross-validation. PMID:18522479

  4. Assessing the toxic effects of ethylene glycol ethers using Quantitative Structure Toxicity Relationship models

    SciTech Connect

    Ruiz, Patricia; Mumtaz, Moiz; Gombar, Vijay

    2011-07-15

    Experimental determination of toxicity profiles consumes a great deal of time, money, and other resources. Consequently, businesses, societies, and regulators strive for reliable alternatives such as Quantitative Structure Toxicity Relationship (QSTR) models to fill gaps in toxicity profiles of compounds of concern to human health. The use of glycol ethers and their health effects have recently attracted the attention of international organizations such as the World Health Organization (WHO). The board members of Concise International Chemical Assessment Documents (CICAD) recently identified inadequate testing as well as gaps in toxicity profiles of ethylene glycol mono-n-alkyl ethers (EGEs). The CICAD board requested the ATSDR Computational Toxicology and Methods Development Laboratory to conduct QSTR assessments of certain specific toxicity endpoints for these chemicals. In order to evaluate the potential health effects of EGEs, CICAD proposed a critical QSTR analysis of the mutagenicity, carcinogenicity, and developmental effects of EGEs and other selected chemicals. We report here results of the application of QSTRs to assess rodent carcinogenicity, mutagenicity, and developmental toxicity of four EGEs: 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, and 2-butoxyethanol and their metabolites. Neither mutagenicity nor carcinogenicity is indicated for the parent compounds, but these compounds are predicted to be developmental toxicants. The predicted toxicity effects were subjected to reverse QSTR (rQSTR) analysis to identify structural attributes that may be the main drivers of the developmental toxicity potential of these compounds.

  5. Quantitative structure carcinogenicity relationship for detecting structural alerts in nitroso-compounds

    SciTech Connect

    Helguera, Aliuska Morales; Gonzalez, Maykel Perez . E-mail: mpgonzalez76@yahoo.es; Cordeiro, Maria Natalia D.S.; Perez, Miguel Angel Cabrera

    2007-06-01

    Prevention of environmentally induced cancers is a major health problem of which solutions depend on the rapid and accurate screening of potential chemical hazards. Lately, theoretical approaches such as the one proposed here - Quantitative Structure-Activity Relationship (QSAR) - are increasingly used for assessing the risks of environmental chemicals, since they can markedly reduce costs, avoid animal testing, and speed up policy decisions. This paper reports a QSAR study based on the Topological Substructural Molecular Design (TOPS-MODE) approach, aiming at predicting the rodent carcinogenicity of a set of nitroso-compounds selected from the Carcinogenic Potency Data Base (CPDB). The set comprises nitrosoureas (14 chemicals), N-nitrosamines (18 chemicals) C-nitroso-compounds (1 chemical), nitrosourethane (1 chemical) and nitrosoguanidine (1 chemical), which have been bioassayed in male rat using gavage as the route of administration. Here we are especially concerned in gathering the role of both parameters on the carcinogenic activity of this family of compounds. First, the regression model was derived, upon removal of one identified nitrosamine outlier, and was able to account for more than 84% of the variance in the experimental activity. Second, the TOPS-MODE approach afforded the bond contributions - expressed as fragment contributions to the carcinogenic activity - that can be interpreted and provide tools for better understanding the mechanisms of carcinogenesis. Finally, and most importantly, we demonstrate the potentialities of this approach towards the recognition of structural alerts for carcinogenicity predictions.

  6. Quantitative structure-retention relationship modeling of gas chromatographic retention times based on thermodynamic data.

    PubMed

    Ebrahimi-Najafabadi, Heshmatollah; McGinitie, Teague M; Harynuk, James J

    2014-09-01

    Thermodynamic parameters of ΔH(T0), ΔS(T0), and ΔCP for 156 compounds comprising alkanes, alkyl halides and alcohols were determined for a 5% phenyl 95% methyl stationary phase. The determination of thermodynamic parameters relies on a Nelder-Mead simplex optimization to rapidly obtain the parameters. Two methodologies of external and leave one out cross validations were applied to assess the robustness of the estimations of thermodynamic parameters. The largest absolute errors in predicted retention time across all temperature ramps and all compounds were 1.5 and 0.3s for external and internal sets, respectively. The possibility of an in silico extension of the thermodynamic library was tested using a quantitative structure-retention relationship (QSRR) methodology. The estimated thermodynamic parameters were utilized to develop QSRR models. Individual partial least squares (PLS) models were developed for each of the three classes of the molecules. R(2) values for the test sets of all models across all temperature ramps were larger than 0.99 and the average of relative errors in retention time predictions of the test sets for alkanes, alcohols, and alkyl halides were 1.8%, 2.4%, and 2.5%, respectively. PMID:25035236

  7. Quantitative structure-activity relationships for the mutagenicity of propylene oxides with Salmonella.

    PubMed

    Hooberman, B H; Chakraborty, P K; Sinsheimer, J E

    1993-04-01

    A quantitative structure-activity relationship approach was used to investigate the mutagenicity of a series of seventeen-monosubstituted propylene oxides in Salmonella typhimurium strains TA100 and TA1535. Mutagenicity in strain TA100, using a liquid suspension assay, was found to correlate with chemical reactivity, as measured by the rates of reaction with two model bionucleophiles, nicotinamide and 4-(4-nitrobenzyl)pyridine. However, since the reactivity of three of the epoxides did not correlate to their Taft sigma * values, as a measure of the electronic effects of substituent groups, neither was their mutagenicity predicted by this substituent constant. The relative mutagenicity for the propylene oxides was different in the liquid suspension assay than that determined by the standard plate incorporation assay and also differed between the two bacterial strains. The assay differences were attributed to epoxide stability. The differences between strains was observed to be due to the response of the error-prone repair system, found only in TA100, to the stronger alkylating agents. PMID:7680427

  8. Utilization of quantitative structure-activity relationships (QSARs) in risk assessment: Alkylphenols

    SciTech Connect

    Beck, B.D.; Toole, A.P.; Callahan, B.G.; Siddhanti, S.K. )

    1991-12-01

    Alkylphenols are a class of environmentally pervasive compounds, found both in natural (e.g., crude oils) and in anthropogenic (e.g., wood tar, coal gasification waste) materials. Despite the frequent environmental occurrence of these chemicals, there is a limited toxicity database on alkylphenols. The authors have therefore developed a 'toxicity equivalence approach' for alkylphenols which is based on their ability to inhibit, in a specific manner, the enzyme cyclooxygenase. Enzyme-inhibiting ability for individual alkylphenols can be estimated based on the quantitative structure-activity relationship developed by Dewhirst (1980) and is a function of the free hydroxyl group, electron-donating ring substituents, and hydrophobic aromatic ring substituents. The authors evaluated the toxicological significance of cyclooxygenase inhibition by comparison of the inhibitory capacity of alkylphenols with the inhibitory capacity of acetylsalicylic acid, or aspirin, a compound whose low-level effects are due to cyclooxygenase inhibition. Since nearly complete absorption for alkylphenols and aspirin is predicted, based on estimates of hydrophobicity and fraction of charged molecules at gastrointestinal pHs, risks from alkylphenols can be expressed directly in terms of 'milligram aspirin equivalence,' without correction for absorption differences. They recommend this method for assessing risks of mixtures of alkylphenols, especially for those compounds with no chronic toxicity data.38 references.

  9. Development of quantitative interspecies toxicity relationship modeling of chemicals to fish.

    PubMed

    Fatemi, M H; Mousa Shahroudi, E; Amini, Z

    2015-09-01

    In this work, quantitative interspecies-toxicity relationship methodologies were used to improve the prediction power of interspecies toxicity model. The most relevant descriptors selected by stepwise multiple linear regressions and toxicity of chemical to Daphnia magna were used to predict the toxicities of chemicals to fish. Modeling methods that were used for developing linear and nonlinear models were multiple linear regression (MLR), random forest (RF), artificial neural network (ANN) and support vector machine (SVM). The obtained results indicate the superiority of SVM model over other models. Robustness and reliability of the constructed SVM model were evaluated by using the leave-one-out cross-validation method (Q(2)=0.69, SPRESS=0.822) and Y-randomization test (R(2)=0.268 for 30 trail). Furthermore, the chemical applicability domains of these models were determined via leverage approach. The developed SVM model was used for the prediction of toxicity of 46 compounds that their experimental toxicities to a fish were not being reported earlier from their toxicities to D. magna and relevant molecular descriptors. PMID:26002421

  10. [Construction of the quantitative structure retention relationship of cefdinir related substances].

    PubMed

    Wang, Chen; Li, Jin; Feng, Yan-chun; Liu, Ying; Hu, Chang-qin

    2015-09-01

    The molecular descriptors of impurities with known structure in cefdinir were calculated, selected and associated with the chromatographic retention behavior to establish a model. This quantitative structure retention relationships (QSRR) model for the related substances of cefdinir was established under specific chromatographic condition and verified by other impurities. 12 molecular descriptors were used to establish the QSRR model, F_AFRBWF, Blbn_J, SsCH3, SssCH2, SsNH2, SssNH, SssS, SHdCH2, EEM_AFc, EEM_AFpl, EEM_XFpl and Pi_MaxQ. The relativity between true values and predictions in QSRR of cefdinir is R2 = 0.9836 (n = 18), ΔRRT is no more than 0.154, as 10.17% in RRT. The results indicate that the QSRR model for the related substances of cefdinir can be used to evaluate the analysis methods for related substances and predict the chromatographic behavior of new impurities, which will provide a new way for the evaluation of the effectiveness for drug quality control. PMID:26757554

  11. Arsenate (As V) in water: quantitative sensitivity relationships among biomarker, ecotoxicity and genotoxicity endpoints.

    PubMed

    Silva, Valéria C; Almeida, Sônia M; Resgalla, Charrid; Masfaraud, Jean-François; Cotelle, Sylvie; Radetski, Claudemir M

    2013-06-01

    It is useful to test ecotoxicity and genotoxicity endpoints in the environmental impact assessment. Here, we compare and discuss ecotoxicity and genotoxicity effects in organisms in response to exposure to arsenate (As V) in solution. Eco(geno)toxicity responses in Aliivibrio fischeri, Lytechinus variegatus, Daphnia magna, Skeletonema costatum and Vicia faba were analyzed by assessing different endpoints: biomass growth, peroxidase activity, mitotic index, micronucleus frequency, and lethality in accordance with the international protocols. Quantitative sensitivity relationships (QSR) between these endpoints were established in order to rank endpoint sensitivity. The results for the QSR values based on the lowest observed effect concentration (LOEC) ratios varied from 2 (for ratio of root peroxidase activity to leaf peroxidase activity) to 2286 (for ratio of higher plant biomass growth to root peroxidase activity). The QSR values allowed the following sensitivity ranking to be established: higher plant enzymatic activity>daphnids≈echinoderms>bacteria≈algae>higher plant biomass growth. The LOEC values for the mitotic index and micronucleus frequency (LOEC=0.25mgAsL(-1)) were similar to the lowest LOEC values observed in aquatic organisms. This approach to the QSR of different endpoints could form the basis for monitoring and predicting early effects of pollutants before they give rise to significant changes in natural community structures. PMID:23597676

  12. Quantitative structure-activity relationships and the prediction of MHC supermotifs.

    PubMed

    Doytchinova, Irini A; Guan, Pingping; Flower, Darren R

    2004-12-01

    The underlying assumption in quantitative structure-activity relationship (QSAR) methodology is that related chemical structures exhibit related biological activities. We review here two QSAR methods in terms of their applicability for human MHC supermotif definition. Supermotifs are motifs that characterise binding to more than one allele. Supermotif definition is the initial in silico step of epitope-based vaccine design. The first QSAR method we review here--the additive method--is based on the assumption that the binding affinity of a peptide depends on contributions from both amino acids and the interactions between them. The second method is a 3D-QSAR method: comparative molecular similarity indices analysis (CoMSIA). Both methods were applied to 771 peptides binding to 9 HLA alleles. Five of the alleles (A*0201, A*0202, A*0203, A*0206 and A*6802) belong to the HLA-A2 superfamily and the other four (A*0301, A*1101, A*3101 and A*6801) to the HLA-A3 superfamily. For each superfamily, supermotifs defined by the two QSAR methods agree closely and are supported by many experimental data. PMID:15542370

  13. Docking and quantitative structure-activity relationship of oxadiazole derivates as inhibitors of GSK3β.

    PubMed

    Quesada-Romero, Luisa; Caballero, Julio

    2014-02-01

    The binding modes of 42 oxadiazole derivates inside glycogen synthase kinase 3 beta (GSK3β were determined using docking experiments; thus, the preferred active conformations of these inhibitors are proposed. We found that these compounds adopt a scorpion-shaped conformation and they accept a hydrogen bond (HB) from the residue Val135 of the GSK3β ATP-binding site hinge region. In addition, quantitative structure-activity relationship (QSAR) models were constructed to explain the trend of the GSK3β inhibitory activities for the studied compounds. In a first approach, three-dimensional (3D) vectors were calculated using docking conformations and, by using multiple-linear regression, we assessed that GETAWAY vectors were able to describe the reported biological activities. In other QSAR approach, SMILES-based optimal descriptors were calculated. The best model included three-SMILES elements SSSβ leading to the identification of key molecular features that contribute to a high GSK3β inhibitory activity. PMID:24081608

  14. Consensus Genome-Wide Expression Quantitative Trait Loci and Their Relationship with Human Complex Trait Disease.

    PubMed

    Yu, Chen-Hsin; Pal, Lipika R; Moult, John

    2016-07-01

    Most of the risk loci identified from genome-wide association (GWA) studies do not provide direct information on the biological basis of a disease or on the underlying mechanisms. Recent expression quantitative trait locus (eQTL) association studies have provided information on genetic factors associated with gene expression variation. These eQTLs might contribute to phenotype diversity and disease susceptibility, but interpretation is handicapped by low reproducibility of the expression results. To address this issue, we have generated a set of consensus eQTLs by integrating publicly available data for specific human populations and cell types. Overall, we find over 4000 genes that are involved in high-confidence eQTL relationships. To elucidate the role that eQTLs play in human common diseases, we matched the high-confidence eQTLs to a set of 335 disease risk loci identified from the Wellcome Trust Case Control Consortium GWA study and follow-up studies for 7 human complex trait diseases-bipolar disorder (BD), coronary artery disease (CAD), Crohn's disease (CD), hypertension (HT), rheumatoid arthritis (RA), type 1 diabetes (T1D), and type 2 diabetes (T2D). The results show that the data are consistent with ∼50% of these disease loci arising from an underlying expression change mechanism. PMID:27428252

  15. Deep neural nets as a method for quantitative structure-activity relationships.

    PubMed

    Ma, Junshui; Sheridan, Robert P; Liaw, Andy; Dahl, George E; Svetnik, Vladimir

    2015-02-23

    Neural networks were widely used for quantitative structure-activity relationships (QSAR) in the 1990s. Because of various practical issues (e.g., slow on large problems, difficult to train, prone to overfitting, etc.), they were superseded by more robust methods like support vector machine (SVM) and random forest (RF), which arose in the early 2000s. The last 10 years has witnessed a revival of neural networks in the machine learning community thanks to new methods for preventing overfitting, more efficient training algorithms, and advancements in computer hardware. In particular, deep neural nets (DNNs), i.e. neural nets with more than one hidden layer, have found great successes in many applications, such as computer vision and natural language processing. Here we show that DNNs can routinely make better prospective predictions than RF on a set of large diverse QSAR data sets that are taken from Merck's drug discovery effort. The number of adjustable parameters needed for DNNs is fairly large, but our results show that it is not necessary to optimize them for individual data sets, and a single set of recommended parameters can achieve better performance than RF for most of the data sets we studied. The usefulness of the parameters is demonstrated on additional data sets not used in the calibration. Although training DNNs is still computationally intensive, using graphical processing units (GPUs) can make this issue manageable. PMID:25635324

  16. Quantitative structure-activity relationships for the toxicity of nitrobenzenes to Tetrahymena thermophila.

    PubMed

    Xu, Jing-Bo; Jing, Ti-Song; Pauli, W; Berger, S

    2002-01-01

    In this study IGC50 (50% inhibitory growth concentration) values of 26 nitrobenzenes were determined for population growth endpoint of Tetrahymena thermophila. The toxicity order of the observed compounds has been found as follows: dinitro compounds > mono-nitro compounds; dichloronitrobenzenes > monochloronitrobenzenes; and meta-substituted nitrobenzenes > ortho-/para-substituted nitrobenzenes (NT, NPh, NAnis) except for the dinitrobenzenes and nitroanilines (DNB, NAn). Quantitative structure activity relationships (QSARs) were developed using log of the inverse of the IGC50 (logIGC50(-1)) in mole liter as the dependent variable and six molecular descriptors--logP, 1X(V), I, K alpha, sigma sigma- and E(LUMO) as the independent variables. Through multiplicate regression analysis, one best equation was obtained: log IGC50(-1) = 2.93 + 0.830sigma sigma- + 0.350I, n = 26, r = 0.923, r2 = 0.852, s = 0.265, f = 66.4 The equation was used to estimate IGC50 for seven analogues. PMID:12046656

  17. The Relationship between Shyness and Internet Addiction: A Quantitative Study on Middle and Post Secondary School Students

    ERIC Educational Resources Information Center

    Hollingsworth, W. Craig

    2005-01-01

    This small scale quantitative study looks into the relationship between shyness and internet addiction in middle school students. This study has been conducted on the belief that shyness is a possible predictor of Internet Addiction. To prove this hypothesis a questionnaire was created and distributed to 53 middle school students and 159 post…

  18. Three dimensional quantitative structure-activity relationships of sulfonamides binding monoclonal antibody by comparative molecular field analysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The three-dimensional quantitative structure-activity relationship (3D-QSAR) model of sulfonamide analogs, binding a monoclonal antibody (MabSMR) produced against sulfamerazine was carried out by comparative molecular field analysis (CoMFA). The affinities of MabSMR, expressed as Log10IC50, for 17 ...

  19. Structure-property evolution during polymer crystallization

    NASA Astrophysics Data System (ADS)

    Arora, Deepak

    The main theme of this research is to understand the structure-property evolution during crystallization of a semicrystalline thermoplastic polymer. A combination of techniques including rheology, small angle light scattering, differential scanning calorimetry and optical microscopy are applied to follow the mechanical and optical properties along with crystallinity and the morphology. Isothermal crystallization experiments on isotactic poly-1-butene at early stages of spherulite growth provide quantitative information about nucleation density, volume fraction of spherulites and their crystallinity, and the mechanism of connecting into a sample spanning structure. Optical microscopy near the fluid-to-solid transition suggests that the transition, as determined by time-resolved mechanical spectroscopy, is not caused by packing/jamming of spherulites but by the formation of a percolating network structure. The effect of strain, Weissenberg number (We ) and specific mechanical work (w) on rate of crystallization (nucleation followed by growth) and on growth of anisotropy was studied for shear-induced crystallization of isotactic poly-1-butene. The samples were sheared for a finite strain at the beginning of the experiment and then crystallized without further flow (Janeschitz-Kriegl protocol). Strain requirements to attain steady state/leveling off of the rate of crystallization were found to be much larger than the strain needed to achieve steady state of flow. The large strain and We>1 criteria were also observed for morphological transition from spherulitic growth to oriented growth. An apparatus for small angle light scattering (SALS) and light transmission measurements under shear was built and tested at the University of Massachusetts Amherst. As a new development, the polarization direction can be rotated by a liquid crystal polarization rotator (LCPR) with a short response time of 20 ms. The experiments were controlled and analyzed with a LabVIEW(TM) based

  20. Toward a class-independent quantitative structure--activity relationship model for uncouplers of oxidative phosphorylation.

    PubMed

    Spycher, Simon; Smejtek, Pavel; Netzeva, Tatiana I; Escher, Beate I

    2008-04-01

    A mechanistically based quantitative structure-activity relationship (QSAR) for the uncoupling activity of weak organic acids has been derived. The analysis of earlier experimental studies suggested that the limiting step in the uncoupling process is the rate with which anions can cross the membrane and that this rate is determined by the height of the energy barrier encountered in the hydrophobic membrane core. We use this mechanistic understanding to develop a predictive model for uncoupling. The translocation rate constants of anions correlate well with the free energy difference between the energy well and the energy barrier, Delta G well-barrier,A (-) , in the membrane calculated by a novel approach to describe internal partitioning in the membrane. An existing data set of 21 phenols measured in an in vitro test system specific for uncouplers was extended by 14 highly diverse compounds. A simple regression model based on the experimental membrane-water partition coefficient and Delta G well-barrier,A (-) showed good predictive power and had meaningful regression coefficients. To establish uncoupler QSARs independent of chemical class, it is necessary to calculate the descriptors for the charged species, as the analogous descriptors of the neutral species showed almost no correlation with the translocation rate constants of anions. The substitution of experimental with calculated partition coefficients resulted in a decrease of the model fit. A particular strength of the current model is the accurate calculation of excess toxicity, which makes it a suitable tool for database screening. The applicability domain, limitations of the model, and ideas for future research are critically discussed. PMID:18358007

  1. Quantitative structure-activity relationships for organophosphates binding to trypsin and chymotrypsin.

    PubMed

    Ruark, Christopher D; Hack, C Eric; Robinson, Peter J; Gearhart, Jeffery M

    2011-01-01

    Organophosphate (OP) nerve agents such as sarin, soman, tabun, and O-ethyl S-[2-(diisopropylamino) ethyl] methylphosphonothioate (VX) do not react solely with acetylcholinesterase (AChE). Evidence suggests that cholinergic-independent pathways over a wide range are also targeted, including serine proteases. These proteases comprise nearly one-third of all known proteases and play major roles in synaptic plasticity, learning, memory, neuroprotection, wound healing, cell signaling, inflammation, blood coagulation, and protein processing. Inhibition of these proteases by OP was found to exert a wide range of noncholinergic effects depending on the type of OP, the dose, and the duration of exposure. Consequently, in order to understand these differences, in silico biologically based dose-response and quantitative structure-activity relationship (QSAR) methodologies need to be integrated. Here, QSAR were used to predict OP bimolecular rate constants for trypsin and α-chymotrypsin. A heuristic regression of over 500 topological/constitutional, geometric, thermodynamic, electrostatic, and quantum mechanical descriptors, using the software Ampac 8.0 and Codessa 2.51 (SemiChem, Inc., Shawnee, KS), was developed to obtain statistically verified equations for the models. General models, using all data subsets, resulted in R(2) values of .94 and .92 and leave-one-out Q(2) values of 0.9 and 0.87 for trypsin and α-chymotrypsin. To validate the general model, training sets were split into independent subsets for test set evaluation. A y-randomization procedure, used to estimate chance correlation, was performed 10,000 times, resulting in mean R(2) values of .24 and .3 for trypsin and α-chymotrypsin. The results show that these models are highly predictive and capable of delineating the complex mechanism of action between OP and serine proteases, and ultimately, by applying this approach to other OP enzyme reactions such as AChE, facilitate the development of biologically based

  2. Quantitative Structure-Pharmacokinetic Relationships for the Prediction of Renal Clearance in Humans

    PubMed Central

    Dave, Rutwij A.

    2015-01-01

    Renal clearance (CLR), a major route of elimination for many drugs and drug metabolites, represents the net result of glomerular filtration, active secretion and reabsorption, and passive reabsorption. The aim of this study was to develop quantitative structure-pharmacokinetic relationships (QSPKR) to predict CLR of drugs or drug-like compounds in humans. Human CLR data for 382 compounds were obtained from the literature. Step-wise multiple linear regression was used to construct QSPKR models for training sets and their predictive performance was evaluated using internal validation (leave-one-out method). All qualified models were validated externally using test sets. QSPKR models were also constructed for compounds in accordance with their 1) net elimination pathways (net secretion, extensive net secretion, net reabsorption, and extensive net reabsorption), 2) net elimination clearances (net secretion clearance, CLSEC; or net reabsorption clearance, CLREAB), 3) ion status, and 4) substrate/inhibitor specificity for renal transporters. We were able to predict 1) CLREAB (Q2 = 0.77) of all compounds undergoing net reabsorption; 2) CLREAB (Q2 = 0.81) of all compounds undergoing extensive net reabsorption; and 3) CLR for substrates and/or inhibitors of OAT1/3 (Q2 = 0.81), OCT2 (Q2 = 0.85), MRP2/4 (Q2 = 0.78), P-gp (Q2 = 0.71), and MATE1/2K (Q2 = 0.81). Moreover, compounds undergoing net reabsorption/extensive net reabsorption predominantly belonged to Biopharmaceutics Drug Disposition Classification System classes 1 and 2. In conclusion, constructed parsimonious QSPKR models can be used to predict CLR of compounds that 1) undergo net reabsorption/extensive net reabsorption and 2) are substrates and/or inhibitors of human renal transporters. PMID:25352657

  3. Relationship between epicardial fat and quantitative coronary artery plaque progression: insights from computer tomography coronary angiography.

    PubMed

    Psaltis, Peter J; Talman, Andrew H; Munnur, Kiran; Cameron, James D; Ko, Brian S H; Meredith, Ian T; Seneviratne, Sujith K; Wong, Dennis T L

    2016-02-01

    Epicardial fat volume (EFV) has been suggested to promote atherosclerotic plaque development in coronary arteries, and has been correlated with both coronary stenosis and acute coronary events. Although associated with progression of coronary calcification burden, a relationship with progression of coronary atheroma volume has not been previously tested. We studied patients who had clinically indicated serial 320-row multi-detector computer tomography coronary angiography with a median 25-month interval. EFV was measured at baseline and follow-up. In vessels with coronary stenosis, quantitative analysis was performed to measure atherosclerotic plaque burden, volume and aggregate plaque volume at baseline and follow-up. The study comprised 64 patients (58.4 ± 12.2 years, 27 males, 192 vessels, 193 coronary segments). 79 (41 %) coronary segments had stenosis at baseline. Stenotic segments were associated with greater baseline EFV than those without coronary stenosis (117.4 ± 45.1 vs. 102.3 ± 51.6 cm(3), P = 0.046). 46 (24 %) coronary segments displayed either new plaque formation or progression of adjusted plaque burden at follow-up. These were associated with higher baseline EFV than segments without stenosis or those segments that had stenoses that did not progress (128.7 vs. 101.0 vs. 106.7 cm(3) respectively, P = 0.006). On multivariate analysis, baseline EFV was the only independent predictor of coronary atherosclerotic plaque progression or new development (P = 0.014). High baseline EFV is associated with the presence of coronary artery stenosis and plaque volume progression. Accumulation of EFV may be implicated in the evolution and progression of coronary atheroma. PMID:26335371

  4. Design and prediction of new acetylcholinesterase inhibitor via quantitative structure activity relationship of huprines derivatives.

    PubMed

    Zhang, Shuqun; Hou, Bo; Yang, Huaiyu; Zuo, Zhili

    2016-05-01

    Acetylcholinesterase (AChE) is an important enzyme in the pathogenesis of Alzheimer's disease (AD). Comparative quantitative structure-activity relationship (QSAR) analyses on some huprines inhibitors against AChE were carried out using comparative molecular field analysis (CoMFA), comparative molecular similarity indices analysis (CoMSIA), and hologram QSAR (HQSAR) methods. Three highly predictive QSAR models were constructed successfully based on the training set. The CoMFA, CoMSIA, and HQSAR models have values of r (2) = 0.988, q (2) = 0.757, ONC = 6; r (2) = 0.966, q (2) = 0.645, ONC = 5; and r (2) = 0.957, q (2) = 0.736, ONC = 6. The predictabilities were validated using an external test sets, and the predictive r (2) values obtained by the three models were 0.984, 0.973, and 0.783, respectively. The analysis was performed by combining the CoMFA and CoMSIA field distributions with the active sites of the AChE to further understand the vital interactions between huprines and the protease. On the basis of the QSAR study, 14 new potent molecules have been designed and six of them are predicted to be more active than the best active compound 24 described in the literature. The final QSAR models could be helpful in design and development of novel active AChE inhibitors. PMID:26832327

  5. Quantitative structure-activity relationships (QSARs) for the transformation of organic micropollutants during oxidative water treatment.

    PubMed

    Lee, Yunho; von Gunten, Urs

    2012-12-01

    Various oxidants such as chlorine, chlorine dioxide, ferrate(VI), ozone, and hydroxyl radicals can be applied for eliminating organic micropollutant by oxidative transformation during water treatment in systems such as drinking water, wastewater, and water reuse. Over the last decades, many second-order rate constants (k) have been determined for the reaction of these oxidants with model compounds and micropollutants. Good correlations (quantitative structure-activity relationships or QSARs) are often found between the k-values for an oxidation reaction of closely related compounds (i.e. having a common organic functional group) and substituent descriptor variables such as Hammett or Taft sigma constants. In this study, we developed QSARs for the oxidation of organic and some inorganic compounds and organic micropollutants transformation during oxidative water treatment. A number of 18 QSARs were developed based on overall 412 k-values for the reaction of chlorine, chlorine dioxide, ferrate, and ozone with organic compounds containing electron-rich moieties such as phenols, anilines, olefins, and amines. On average, 303 out of 412 (74%) k-values were predicted by these QSARs within a factor of 1/3-3 compared to the measured values. For HO(·) reactions, some principles and estimation methods of k-values (e.g. the Group Contribution Method) are discussed. The developed QSARs and the Group Contribution Method could be used to predict the k-values for various emerging organic micropollutants. As a demonstration, 39 out of 45 (87%) predicted k-values were found within a factor 1/3-3 compared to the measured values for the selected emerging micropollutants. Finally, it is discussed how the uncertainty in the predicted k-values using the QSARs affects the accuracy of prediction for micropollutant elimination during oxidative water treatment. PMID:22939392

  6. Quantitative Structure--Activity Relationship (QSAR) for the Oxidation of Trace Organic Contaminants by Sulfate Radical.

    PubMed

    Xiao, Ruiyang; Ye, Tiantian; Wei, Zongsu; Luo, Shuang; Yang, Zhihui; Spinney, Richard

    2015-11-17

    The sulfate radical anion (SO4•–) based oxidation of trace organic contaminants (TrOCs) has recently received great attention due to its high reactivity and low selectivity. In this study, a meta-analysis was conducted to better understand the role of functional groups on the reactivity between SO4•– and TrOCs. The results indicate that compounds in which electron transfer and addition channels dominate tend to exhibit a faster second-order rate constants (kSO4•–) than that of H–atom abstraction, corroborating the SO4•– reactivity and mechanisms observed in the individual studies. Then, a quantitative structure activity relationship (QSAR) model was developed using a sequential approach with constitutional, geometrical, electrostatic, and quantum chemical descriptors. Two descriptors, ELUMO and EHOMO energy gap (ELUMO–EHOMO) and the ratio of oxygen atoms to carbon atoms (#O:C), were found to mechanistically and statistically affect kSO4•– to a great extent with the standardized QSAR model: ln kSO4•– = 26.8–3.97 × #O:C – 0.746 × (ELUMO–EHOMO). In addition, the correlation analysis indicates that there is no dominant reaction channel for SO4•– reactions with various structurally diverse compounds. Our QSAR model provides a robust predictive tool for estimating emerging micropollutants removal using SO4•– during wastewater treatment processes. PMID:26451961

  7. Quantitative structure-activity relationships (QSARs) using the novel marine algal toxicity data of phenols.

    PubMed

    Ertürk, M Doğa; Saçan, Melek Türker; Novic, Marjana; Minovski, Nikola

    2012-09-01

    The present study reports for the first time in its entirety the toxicity of 30 phenolic compounds to marine alga Dunaliella tertiolecta. Toxicity of polar narcotics and respiratory uncouplers was strongly correlated to hydrophobicity as described by the logarithm of the octanol/water partition coefficient (Log P). Compounds expected to act by more reactive mechanisms, particularly hydroquinones, were shown to have toxicity in excess of that predicted by Log P. A quality quantitative structure-activity relationship (QSAR) was obtained with Log P and a 2D autocorrelation descriptor weighted by atomic polarizability (MATS3p) only after the removal of hydroquinones from the data set. In an attempt to model the whole data set including hydroquinones, 3D descriptors were included in the modeling process and three quality QSARs were developed using multiple linear regression (MLR). One of the most significant results of the present study was the superior performance of the consensus MLR model, obtained by averaging the predictions from each individual linear model, which provided excellent prediction accuracy for the test set (Q(test)²=0.94). The four-parameter Counter Propagation Artificial Neural Network (CP ANN) model, which was constructed using four out of six descriptors that appeared in the linear models, also provided an excellent external predictivity (Q(test)²=0.93). The proposed algal QSARs were further tested in their predictivity using an external set comprising toxicity data of 44 chemicals on freshwater alga Pseudokirchneriella subcapitata. The two-parameter global model employing a 3D descriptor (Mor24m) and a charge-related descriptor (C(ortho)) not only had high external predictivity (Q(ext)²=0.74), but it also had excellent external data set coverage (%97). PMID:23085159

  8. Quantitative structure activity relationship and risk analysis of some pesticides in the goat milk.

    PubMed

    Muhammad, Faqir; Awais, Mian Muhammad; Akhtar, Masood; Anwar, Muhammad Irfan

    2013-01-01

    The detection and quantification of different pesticides in the goat milk samples collected from different localities of Faisalabad, Pakistan was performed by HPLC using solid phase microextraction. The analysis showed that about 50% milk samples were contaminated with pesticides. The mean±SEM levels (ppm) of cyhalothrin, endosulfan, chlorpyrifos and cypermethrin were 0.34±0.007, 0.063±0.002, 0.034±0.002 and 0.092±0.002, respectively; whereas, methyl parathion was not detected in any of the analyzed samples. Quantitative structure activity relationship (QSAR) models were suggested to predict the residues of unknown pesticides in the goat milk using their known physicochemical characteristics including molecular weight (MW), melting point (MP), and log octanol to water partition coefficient (Ko/w) in relation to the characteristics such as pH, % fat, specific gravity and refractive index of goat milk. The analysis revealed good correlation coefficient (R2 = 0.985) for goat QSAR model. The coefficients for Ko/w and refractive index for the studied pesticides were higher in goat milk. This suggests that these are better determinants for pesticide residue prediction in the milk of these animals. Based upon the determined pesticide residues and their provisional tolerable daily intakes, risk analysis was also conducted which showed that daily intake levels of pesticide residues including cyhalothrin, chlorpyrifos and cypermethrin in present study are 2.68, 5.19 and 2.71 times higher, respectively in the goat milk. This intake of pesticide contaminated milk might pose health hazards to humans in this locality. PMID:23369514

  9. Quantitative structure–activity relationship analysis of the pharmacology of para-substituted methcathinone analogues

    PubMed Central

    Bonano, J S; Banks, M L; Kolanos, R; Sakloth, F; Barnier, M L; Glennon, R A; Cozzi, N V; Partilla, J S; Baumann, M H; Negus, S S

    2015-01-01

    Background and Purpose Methcathinone (MCAT) is a potent monoamine releaser and parent compound to emerging drugs of abuse including mephedrone (4-CH3 MCAT), the para-methyl analogue of MCAT. This study examined quantitative structure–activity relationships (QSAR) for MCAT and six para-substituted MCAT analogues on (a) in vitro potency to promote monoamine release via dopamine and serotonin transporters (DAT and SERT, respectively), and (b) in vivo modulation of intracranial self-stimulation (ICSS), a behavioural procedure used to evaluate abuse potential. Neurochemical and behavioural effects were correlated with steric (Es), electronic (σp) and lipophilic (πp) parameters of the para substituents. Experimental Approach For neurochemical studies, drug effects on monoamine release through DAT and SERT were evaluated in rat brain synaptosomes. For behavioural studies, drug effects were tested in male Sprague-Dawley rats implanted with electrodes targeting the medial forebrain bundle and trained to lever-press for electrical brain stimulation. Key Results MCAT and all six para-substituted analogues increased monoamine release via DAT and SERT and dose- and time-dependently modulated ICSS. In vitro selectivity for DAT versus SERT correlated with in vivo efficacy to produce abuse-related ICSS facilitation. In addition, the Es values of the para substituents correlated with both selectivity for DAT versus SERT and magnitude of ICSS facilitation. Conclusions and Implications Selectivity for DAT versus SERT in vitro is a key determinant of abuse-related ICSS facilitation by these MCAT analogues, and steric aspects of the para substituent of the MCAT scaffold (indicated by Es) are key determinants of this selectivity. PMID:25438806

  10. Elucidating Quantitative Stability/Flexibility Relationships Within Thioredoxin and its Fragments Using a Distance Constraint Model

    PubMed Central

    Jacobs, Donald J.; Livesay, Dennis R.; Hules, Jeremy; Tasayco, Maria Luisa

    2015-01-01

    Numerous quantitative stability/flexibility relationships, within Escherichia coli thioredoxin (Trx) and its fragments are determined using a minimal distance constraint model (DCM). A one-dimensional free energy landscape as a function of global flexibility reveals Trx to fold in a low-barrier two-state process, with a voluminous transition state. Near the folding transition temperature, the native free energy basin is markedly skewed to allow partial unfolded forms. Under native conditions the skewed shape is lost, and the protein forms a compact structure with some flexibility. Predictions on ten Trx fragments are generally consistent with experimental observations that they are disordered, and that complementary fragments reconstitute. A hierarchical unfolding pathway is uncovered using an exhaustive computational procedure of breaking interfacial cross-linking hydrogen bonds that span over a series of fragment dissociations. The unfolding pathway leads to a stable core structure (residues 22–90), predicted to act as a kinetic trap. Direct connection between degree of rigidity within molecular structure and non-additivity of free energy is demonstrated using a thermodynamic cycle involving fragments and their hierarchical unfolding pathway. Additionally, the model provides insight about molecular cooperativity within Trx in its native state, and about intermediate states populating the folding/unfolding pathways. Native state cooperativity correlation plots highlight several flexibly correlated regions, giving insight into the catalytic mechanism that facilitates access to the active site disulfide bond. Residual native cooperativity correlations are present in the core substructure, suggesting that Trx can function when it is partly unfolded. This natively disordered kinetic trap, interpreted as a molten globule, has a wide temperature range of metastability, and it is identified as the “slow intermediate state” observed in kinetic experiments. These

  11. Quantitative structure activity relationship and risk analysis of some pesticides in the goat milk

    PubMed Central

    2013-01-01

    The detection and quantification of different pesticides in the goat milk samples collected from different localities of Faisalabad, Pakistan was performed by HPLC using solid phase microextraction. The analysis showed that about 50% milk samples were contaminated with pesticides. The mean±SEM levels (ppm) of cyhalothrin, endosulfan, chlorpyrifos and cypermethrin were 0.34±0.007, 0.063±0.002, 0.034±0.002 and 0.092±0.002, respectively; whereas, methyl parathion was not detected in any of the analyzed samples. Quantitative structure activity relationship (QSAR) models were suggested to predict the residues of unknown pesticides in the goat milk using their known physicochemical characteristics including molecular weight (MW), melting point (MP), and log octanol to water partition coefficient (Ko/w) in relation to the characteristics such as pH, % fat, specific gravity and refractive index of goat milk. The analysis revealed good correlation coefficient (R2 = 0.985) for goat QSAR model. The coefficients for Ko/w and refractive index for the studied pesticides were higher in goat milk. This suggests that these are better determinants for pesticide residue prediction in the milk of these animals. Based upon the determined pesticide residues and their provisional tolerable daily intakes, risk analysis was also conducted which showed that daily intake levels of pesticide residues including cyhalothrin, chlorpyrifos and cypermethrin in present study are 2.68, 5.19 and 2.71 times higher, respectively in the goat milk. This intake of pesticide contaminated milk might pose health hazards to humans in this locality. PMID:23369514

  12. Multiobjective optimization in quantitative structure-activity relationships: deriving accurate and interpretable QSARs.

    PubMed

    Nicolotti, Orazio; Gillet, Valerie J; Fleming, Peter J; Green, Darren V S

    2002-11-01

    Deriving quantitative structure-activity relationship (QSAR) models that are accurate, reliable, and easily interpretable is a difficult task. In this study, two new methods have been developed that aim to find useful QSAR models that represent an appropriate balance between model accuracy and complexity. Both methods are based on genetic programming (GP). The first method, referred to as genetic QSAR (or GPQSAR), uses a penalty function to control model complexity. GPQSAR is designed to derive a single linear model that represents an appropriate balance between the variance and the number of descriptors selected for the model. The second method, referred to as multiobjective genetic QSAR (MoQSAR), is based on multiobjective GP and represents a new way of thinking of QSAR. Specifically, QSAR is considered as a multiobjective optimization problem that comprises a number of competitive objectives. Typical objectives include model fitting, the total number of terms, and the occurrence of nonlinear terms. MoQSAR results in a family of equivalent QSAR models where each QSAR represents a different tradeoff in the objectives. A practical consideration often overlooked in QSAR studies is the need for the model to promote an understanding of the biochemical response under investigation. To accomplish this, chemically intuitive descriptors are needed but do not always give rise to statistically robust models. This problem is addressed by the addition of a further objective, called chemical desirability, that aims to reward models that consist of descriptors that are easily interpretable by chemists. GPQSAR and MoQSAR have been tested on various data sets including the Selwood data set and two different solubility data sets. The study demonstrates that the MoQSAR method is able to find models that are at least as good as models derived using standard statistical approaches and also yields models that allow a medicinal chemist to trade statistical robustness for chemical

  13. Structural Properties of Mismatched Alloys

    NASA Astrophysics Data System (ADS)

    Mousseau, Normand

    The problem of understanding the local structure of disordered alloys has been around for a long time. In this thesis, I look more specifically at the effect of size-mismatch disorder in binary alloys under many forms: metallic and semiconductor alloys, bulk and surfaces, two and three dimensional systems. I have studied the limitations of a central-force model (CFM) and an embedded-atom potential (EAM) in describing the local structure of binary metallic alloys composed of Ag, Au, Cu, Ni, Pd, or Pt. Although an analytical model developed using the CFM explains qualitatively well the experimental and numerical results, in many cases, it is important to add electronic density effects through a more sophisticated potential like EAM in order to agree quantitatively with experiment. I have also looked at amorphous and crystalline silicon-germanium alloys. It turns out that the effect of size-mismatch is the same on a crystalline and an amorphous lattice. In the latter case, it can be seen as a perturbation of the much larger disorder due to the amorphisation process. However, the analytical predictions differ, for both the crystalline and amorphous alloys, from the experimental results. If one is to believe the data, there is only one possible explanation for this inconsistency: large amounts of hydrogen are present in the samples used for the measurements. Since the data analysis of EXAFS results is not always straightforward, I have proposed some experiments that could shed light on this problem. One of these experiments would be to look at the (111) surface of a Si-Ge alloy with a scanning tunneling microscope. I also present in this thesis the theoretical predictions for the height distribution at the surface as well as some more general structural information about the relaxation in the network as one goes away from the surface. Finally, I have studied the effect of size -mismatch in a purely two dimensional lattice, looking for mismatch-driven phase transitions

  14. A quantitative model of the relationship between phenotypic variance and heterozygosity at marker loci under partial selfing.

    PubMed Central

    David, P

    1999-01-01

    Negative relationships between allozyme heterozygosity and morphological variance have often been observed and interpreted as evidence for increased developmental stability in heterozygotes. However, inbreeding can also generate such relationships by decreasing heterozygosity at neutral loci and redistributing genetic variance at the same time. I here provide a quantitative genetic model of this process by analogy with heterozygosity-fitness relationships. Inbreeding generates negative heterozygosity-variance relationships irrespective of the genetic architecture of the trait. This holds for fitness traits as well as neutral traits, the effect being stronger for fitness traits under directional dominance or overdominance. The order of magnitude of heterozygosity-variance regressions is compatible with empirical data even with very low inbreeding. Although developmental stability effects cannot be excluded, inbreeding is a parsimonious explanation that should be seriously considered to explain correlations between heterozygosity and both mean and variance of phenotypes in natural populations. PMID:10545474

  15. Quantitative structure-activity relationship models of clinical pharmacokinetics: clearance and volume of distribution.

    PubMed

    Gombar, Vijay K; Hall, Stephen D

    2013-04-22

    Reliable prediction of two fundamental human pharmacokinetic (PK) parameters, systemic clearance (CL) and apparent volume of distribution (Vd), determine the size and frequency of drug dosing and are at the heart of drug discovery and development. Traditionally, estimated CL and Vd are derived from preclinical in vitro and in vivo absorption, distribution, metabolism, and excretion (ADME) measurements. In this paper, we report quantitative structure-activity relationship (QSAR) models for prediction of systemic CL and steady-state Vd (Vdss) from intravenous (iv) dosing in humans. These QSAR models avoid uncertainty associated with preclinical-to-clinical extrapolation and require two-dimensional structure drawing as the sole input. The clean, uniform training sets for these models were derived from the compilation published by Obach et al. (Drug Metab. Disp. 2008, 36, 1385-1405). Models for CL and Vdss were developed using both a support vector regression (SVR) method and a multiple linear regression (MLR) method. The SVR models employ a minimum of 2048-bit fingerprints developed in-house as structure quantifiers. The MLR models, on the other hand, are based on information-rich electro-topological states of two-atom fragments as descriptors and afford reverse QSAR (RQSAR) analysis to help model-guided, in silico modulation of structures for desired CL and Vdss. The capability of the models to predict iv CL and Vdss with acceptable accuracy was established by randomly splitting data into training and test sets. On average, for both CL and Vdss, 75% of test compounds were predicted within 2.5-fold of the value observed and 90% of test compounds were within 5.0-fold of the value observed. The performance of the final models developed from 525 compounds for CL and 569 compounds for Vdss was evaluated on an external set of 56 compounds. The predictions were either better or comparable to those predicted by other in silico models reported in the literature. To

  16. Quantitative structure-activity relationship of the curcumin-related compounds using various regression methods

    NASA Astrophysics Data System (ADS)

    Khazaei, Ardeshir; Sarmasti, Negin; Seyf, Jaber Yousefi

    2016-03-01

    Quantitative structure activity relationship were used to study a series of curcumin-related compounds with inhibitory effect on prostate cancer PC-3 cells, pancreas cancer Panc-1 cells, and colon cancer HT-29 cells. Sphere exclusion method was used to split data set in two categories of train and test set. Multiple linear regression, principal component regression and partial least squares were used as the regression methods. In other hand, to investigate the effect of feature selection methods, stepwise, Genetic algorithm, and simulated annealing were used. In two cases (PC-3 cells and Panc-1 cells), the best models were generated by a combination of multiple linear regression and stepwise (PC-3 cells: r2 = 0.86, q2 = 0.82, pred_r2 = 0.93, and r2m (test) = 0.43, Panc-1 cells: r2 = 0.85, q2 = 0.80, pred_r2 = 0.71, and r2m (test) = 0.68). For the HT-29 cells, principal component regression with stepwise (r2 = 0.69, q2 = 0.62, pred_r2 = 0.54, and r2m (test) = 0.41) is the best method. The QSAR study reveals descriptors which have crucial role in the inhibitory property of curcumin-like compounds. 6ChainCount, T_C_C_1, and T_O_O_7 are the most important descriptors that have the greatest effect. With a specific end goal to design and optimization of novel efficient curcumin-related compounds it is useful to introduce heteroatoms such as nitrogen, oxygen, and sulfur atoms in the chemical structure (reduce the contribution of T_C_C_1 descriptor) and increase the contribution of 6ChainCount and T_O_O_7 descriptors. Models can be useful in the better design of some novel curcumin-related compounds that can be used in the treatment of prostate, pancreas, and colon cancers.

  17. Chromatographic behaviour of ionic liquid cations in view of quantitative structure-retention relationship.

    PubMed

    Molíková, M; Markuszewski, M J; Kaliszan, R; Jandera, P

    2010-02-19

    The availability of ionic liquids (ILs) in wide areas of application often results in the requirement on their determination. The attention is also often focused on the knowledge of hydrophobicity as it plays a key role in the biological effects, in the assessment of environmental risk and in the prediction of the fate of chemicals in the environment and of its influence on retention in RP HPLC. One can get information regarding hydrophobicity and retention mechanism if quantitative structure-retention relationships (QSRRs) are identified. The QSRRs were derived for logarithms of retention factors extrapolated to a pure water (or aqueous buffer) eluent, log k(w), determined for the pyridinium and imidazolium ionic liquid (IL) cations on two C8 (Supelcosil LC-8-DB, Symmetry C8) and two C18 (ACE 5 C18, Symmetry C18) stationary phases with isocratic elution by a mobile phase consisting of acetonitrile/40 mM phosphate buffer. The analyses of ILs were performed at a flow rate of 1 mL min(-1) with UV detection at 218 nm. The QSRRs were derived based on the retention parameters determined experimentally and the structural descriptors of test analytes from molecular modeling. Separations of ILs were obtained with aqueous acetonitrile buffered at pH 3.55 mobile phases. The statistically most significant two-parameter QSRR regression equations related log k(w) to the solvent accessible surface (SAS) of the analytes and the differences in the energies of the highest occupied and the lowest unoccupied molecular orbitals (diffHL). These equations were especially good in case of columns with the highest carbon loads and larger specific surface areas, i.e. Symmetry C18 and Symmetry C8. On the other hand, the column ACE 5 C18 appeared to produce the best quality separations of the ILs studied. The QSRRs derived in the research shed light on the molecular mechanism of HPLC separation of ILs and helped to predict their relative separations. PMID:20060528

  18. The relationship between international trade and non-nutritional health outcomes: A systematic review of quantitative studies.

    PubMed

    Burns, Darren K; Jones, Andrew P; Suhrcke, Marc

    2016-03-01

    Markets throughout the world have been reducing barriers to international trade and investment in recent years. The resulting increases in levels of international trade and investment have subsequently generated research interest into the potential population health impact. We present a systematic review of quantitative studies investigating the relationship between international trade, foreign direct investment and non-nutritional health outcomes. Articles were systematically collected from the SCOPUS, PubMed, EconLit and Web of Science databases. Due to the heterogeneous nature of the evidence considered, the 16 included articles were subdivided into individual level data analyses, selected country analyses and international panel analyses. Articles were then quality assessed using a tool developed as part of the project. Nine of the studies were assessed to be high quality, six as medium quality, and one as low quality. The evidence from the quantitative literature suggests that overall, there appears to be a beneficial association between international trade and population health. There was also evidence of the importance of foreign direct investment, yet a lack of research considering the direction of causality. Taken together, quantitative research into the relationship between trade and non-nutritional health indicates trade to be beneficial, yet this body of research is still in its infancy. Future quantitative studies based on this foundation will provide a stronger basis on which to inform relevant national and international institutions about the health consequences of trade policies. PMID:26820112

  19. Structure-property relationships based on Hammett constants in cyclometalated iridium(III) complexes: their application to the design of a fluorine-free FIrPic-like emitter.

    PubMed

    Frey, Julien; Curchod, Basile F E; Scopelliti, Rosario; Tavernelli, Ivano; Rothlisberger, Ursula; Nazeeruddin, Mohammad K; Baranoff, Etienne

    2014-04-21

    While phosphorescent cyclometalated iridium(iii) complexes have been widely studied, only correlations between oxidation potential EOX and Hammett constant σ, and between the redox gap (ΔEREDOX = EOX-ERED) and emission or absorption wavelength (λabs, λem) have been reported. We present now a quantitative model based on Hammett parameters that rationalizes the effect of the substituents on the properties of cyclometalated iridium(iii) complexes. This simple model allows predicting the apparent redox potentials as well as the electrochemical gap of homoleptic complexes based on phenylpyridine ligands with good accuracy. In particular, the model accounts for the unequal effect of the substituents on both the HOMO and the LUMO energy levels. Consequently, the model is used to anticipate the emission maxima of the corresponding complexes with improved reliability. We demonstrate in a series of phenylpyridine emitters that electron-donating groups can effectively replace electron-withdrawing substituents on the orthometallated phenyl to induce a blue shift of the emission. This result is in contrast with the common approach that uses fluorine to blue shift the emission maximum. Finally, as a proof of concept, we used electron-donating substituents to design a new fluorine-free complex, referred to as EB343, matching the various properties, namely oxidation and reduction potentials, electrochemical gap and emission profile, of the standard sky-blue emitter FIrPic. PMID:24345847

  20. Aquatic toxicity of acrylates and methacrylates: quantitative structure-activity relationships based on Kow and LC50

    SciTech Connect

    Reinert, K.H.

    1987-12-01

    Recent EPA scrutiny of acrylate and methacrylate monomers has resulted in restrictive consent orders and Significant New Use Rules under the Toxic Substances Control Act, based on structure-activity relationships using mouse skin painting studies. The concern is centered on human health issues regarding worker and consumer exposure. Environmental issues, such as aquatic toxicity, are still of concern. Understanding the relationships and environmental risks to aquatic organisms may improve the understanding of the potential risks to human health. This study evaluates the quantitative structure-activity relationships from measured log Kow's and log LC50's for Pimephales promelas (fathead minnow) and Carassius auratus (goldfish). Scientific support of the current regulations is also addressed. Two monomer classes were designated: acrylates and methacrylates. Spearman rank correlation and linear regression were run. Based on this study, an ecotoxicological difference exists between acrylates and methacrylates. Regulatory activities and scientific study should reflect this difference.

  1. Parent-Caregiver Relationships among Beginning Caregivers in Canada: A Quantitative Study

    ERIC Educational Resources Information Center

    Cantin, Gilles; Plante, Isabelle; Coutu, Sylvain; Brunson, Liesette

    2012-01-01

    Despite the importance of establishing meaningful parent-caregiver relationships, little is known about these dyadic relationships among beginning caregivers, who often feel insufficiently prepared to build successful alliances with parents. The present study examined the congruence between parents' and beginning caregivers' perceptions of their…

  2. Relationship Education for Modern Orthodox Jewish Adolescents as a Factor of Marital Satisfaction: A Quantitative Study

    ERIC Educational Resources Information Center

    Maybruch, Chana

    2012-01-01

    Research on the influence of relationship education on marital satisfaction over the last decade has demonstrated positive outcomes for both high school and premarital programs within the general American population. Yet few studies have examined relationship education as a factor of marital satisfaction specifically within the North American…

  3. Relationship between fracture toughness, fracture path, and microstructure of 7050 aluminum alloy. Part 1: Quantitative characterization

    SciTech Connect

    Deshpande, N.U.; Gokhale, A.M.; Denzer, D.K.; Liu, J.

    1998-04-01

    The fracture toughness of Al-Zn-Mg-Cu-based 7XXX aluminum alloys decreases with an increase in the extent of recrystallization. In this contribution, the fracture path of plane-strain fracture-toughness specimens of 7050 alloy (a typical alloy of the 7XXX series) is quantitatively characterized as a function of degree of recrystallization, specimen orientation, and aging condition. The fracture path is quantitatively correlated to fracture toughness, and the bulk microstructural attributes estimated via sterological analysis. In the companion article, these quantitative data are used to develop and verify a multiple-fracture micromechanism-based model that relates the fracture toughness to a number of microstructural parameters of the partially recrystallized alloy plate.

  4. Quantitative Evaluation of a First Year Seminar Program: Relationships to Persistence and Academic Success

    ERIC Educational Resources Information Center

    Jenkins-Guarnieri, Michael A.; Horne, Melissa M.; Wallis, Aaron L.; Rings, Jeffrey A.; Vaughan, Angela L.

    2015-01-01

    In the present study, we conducted a quantitative evaluation of a novel First Year Seminar (FYS) program with a coordinated curriculum implemented at a public, four-year university to assess its potential role in undergraduate student persistence decisions and academic success. Participants were 2,188 first-year students, 342 of whom completed the…

  5. Determination of Some Non-sedating Antihistamines via Their Native Fluorescence and Derivation of Some Quantitative Fluorescence Intensity - Structure Relationships.

    PubMed

    El-Kommos, Michael E; El-Gizawy, Samia M; Atia, Noha N; Hosny, Noha M

    2015-11-01

    A validated simple, novel, and rapid spectrofluorimetric method was developed for the determination of some non-sedating antihistamines (NSAs); namely cetirizine (CTZ), ebastine (EBS), fexofenadine (FXD), and loratadine (LOR). The method is based on measuring the native fluorescence of the cited drugs after protonation in acidic media and studying their quantitative fluorescence intensity - structure relationships. There was a linear relationship between the relative fluorescence intensity and the concentration of the investigated drug. Under the optimal conditions, the linear ranges of calibration curves for the determination of the studied NSAs were 0.10-2.0, 0.20-6.0, and 0.02-1.0 [Formula: see text] for (CTZ, FXD), (EBS), and (LOR); respectively. The factors affecting the protonation of the studied drugs were carefully studied and optimized. The method was validated according to ICH guidelines. The suggested method is applicable for the determination of the four investigated drugs in bulk and pharmaceutical dosage forms with excellent recoveries (97.67-103.80%). Quantitative relationships were found between the relative fluorescence intensities of the protonated drugs and their physicochemical parameters namely: the pKa, log P, connectivity indexes (χ(v)) and their squares. Regression equations (76) were obtained and not previously reported. Six of these equations were highly significant and used for the prediction of RFI of the studied NSAs. PMID:26439930

  6. Quantitative structure-activity relationship modeling on in vitro endocrine effects and metabolic stability involving 26 selected brominated flame retardants.

    PubMed

    Harju, Mikael; Hamers, Timo; Kamstra, Jorke H; Sonneveld, Edwin; Boon, Jan P; Tysklind, Mats; Andersson, Patrik L

    2007-04-01

    In this work, quantitative structure-activity relationships (QSARs) were developed to aid human and environmental risk assessment processes for brominated flame retardants (BFRs). Brominated flame retardants, such as the high-production-volume chemicals polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A, and hexabromocyclododecane, have been identified as potential endocrine disruptors. Quantitative structure-activity relationship models were built based on the in vitro potencies of 26 selected BFRs. The in vitro assays included interactions with, for example, androgen, progesterone, estrogen, and dioxin (aryl hydrocarbon) receptor, plus competition with thyroxine for its plasma carrier protein (transthyretin), inhibition of estradiol sulfation via sulfotransferase, and finally, rate of metabolization. The QSAR modeling, a number of physicochemical parameters were calculated describing the electronic, lipophilic, and structural characteristics of the molecules. These include frontier molecular orbitals, molecular charges, polarities, log octanol/water partitioning coefficient, and two- and three-dimensional molecularproperties. Experimental properties were included and measured for PBDEs, such as their individual ultraviolet spectra (200-320 nm) and retention times on three different high-performance liquid chromatography columns and one nonpolar gas chromatography column. Quantitative structure-activity relationship models based on androgen antagonism and metabolic degradation rates generally gave similar results, suggesting that lower-brominated PBDEs with bromine substitutions in ortho positions and bromine-free meta- and para positions had the highest potencies and metabolic degradation rates. Predictions made for the constituents of the technical flame retardant Bromkal 70-5DE found BDE 17 to be a potent androgen antagonist and BDE 66, which is a relevant PBDE in environmental samples, to be only a weak antagonist. PMID:17447568

  7. NASA Intellectual Property Negotiation Practices and their Relationship to Quantitative Measures of Technology Transfer

    NASA Technical Reports Server (NTRS)

    Bush, Lance B.

    1997-01-01

    In the current political climate NASA must be able to show reliable measures demonstrating successful technology transfer. The currently available quantitative data of intellectual property technology transfer efforts portray a less than successful performance. In this paper, the use of only quantitative values for measurement of technology transfer is shown to undervalue the effort. In addition, NASA's current policy in negotiating intellectual property rights results in undervalued royalty rates. NASA has maintained that it's position of providing public good precludes it from negotiating fair market value for its technology and instead has negotiated for reasonable cost in order to recover processing fees. This measurement issue is examined and recommendations made which include a new policy regarding the intellectual property rights negotiation, and two measures to supplement the intellectual property measures.

  8. Quantitative analysis of the relationship between nucleotide sequence and functional activity.

    PubMed Central

    Stormo, G D; Schneider, T D; Gold, L

    1986-01-01

    Matrices can be used to evaluate sequences for functional activity. Multiple regression can solve for the matrix that gives the best fit between sequence evaluations and quantitative activities. This analysis shows that the best model for context effects on suppression by su2 involves primarily the two nucleotides 3' to the amber codon, and that their contributions are independent and additive. Context effects on 2AP mutagenesis also involve the two nucleotides 3' to the 2AP insertion, but their effects are not independent. In a construct for producing beta-galactosidase, the effects on translational yields of the tri-nucleotide 5' to the initiation codon are dependent on the entire triplet. Models based on these quantitative results are presented for each of the examples. PMID:3092188

  9. [Studies on enzymic browning of potatoes (Solanum tuberosum). II. The quantitative relationship between browning and its causative factors (author's transl)].

    PubMed

    Matheis, G; Belitz, H D

    1977-03-21

    Ten potato varieties, with different rates of browning, were analyzed quantitatively for phenoloxidase, tyrosine, chlorogenic acid, caffeic acid, and for reducing substances (ascorbic acid). The rate of tyrosine turnover was calculated from the data. The fact that the further reactions of the primary oxidation products leading to browning only take place after complete oxidation of the reducing substances, was taken into account. This leads to the same classification of the varieties as does visual observation of the rate of discolouration. Thus a clear relationship between browning and potato constituents is demonstrated. PMID:404776

  10. Benzimidazole-Based Quinazolines: In Vitro Evaluation, Quantitative Structure-Activity Relationship, and Molecular Modeling as Aurora Kinase Inhibitors.

    PubMed

    Sharma, Alka; Luxami, Vijay; Saxena, Sanjai; Paul, Kamaldeep

    2016-03-01

    A series of benzimidazole-based quinazoline derivatives with different substitutions of primary and secondary amines at the C2 position (1-12) were evaluated for their Aurora kinase inhibitory activities. All compounds except for 3 and 6 showed good activity against Aurora kinase inhibitors, with IC50 values in the range of 0.035-0.532 μM. The ligand efficiency (LE) of the compounds with Aurora A kinase was also determined. The structure-activity relationship and the quantitative structure-activity relationship revealed that the Aurora inhibitory activities of these derivatives primarily depend on the different substitutions of the amine present at the C2 position of the quinazoline core. Molecular docking studies in the active binding site also provided theoretical support for the experimental biological data acquired. The current study identifies a novel class of Aurora kinase inhibitors, which can further be used for the treatment of cancer. PMID:26773437

  11. The law of effect and avoidance: a quantitative relationship between response rate and shock-frequency reduction1

    PubMed Central

    De Villiers, Peter A.

    1974-01-01

    Two experiments were conducted to investigate the quantitative relationship between response rate and reinforcement frequency in single and multiple variable-interval avoidance schedules. Responses cancelled delivery of shocks that were scheduled by variable-interval schedules. When shock-frequency reduction was taken as the measure of reinforcement, the relationship between response rate and reinforcement frequency on single variable-interval avoidance schedules was accurately described by Herrnstein's (1970) equation for responding on single variable-interval schedules of positive reinforcement. On multiple variable-interval avoidance schedules with brief components, asymptotic relative response rate matched relative shock-frequency reduction. The results suggest that many interactions between response rates and shock-frequency reduction in avoidance can be understood within the framework of the generalized matching relation, as applied by Herrnstein (1970) to positive reinforcement. PMID:16811740

  12. Finite Element Estimation of Meteorite Structural Properties

    NASA Technical Reports Server (NTRS)

    Hart, Kenneth Arthur

    2015-01-01

    The goal of the project titled Asteroid Threat Assessment at NASA Ames Research Center is to develop risk assessment tools. The expertise in atmospheric entry in the Entry Systems and Technology Division is being used to describe the complex physics of meteor breakup in the atmosphere. The breakup of a meteor is dependent on its structural properties, including homogeneity of the material. The present work describes an 11-week effort in which a literature survey was carried for structural properties of meteoritic material. In addition, the effect of scale on homogeneity isotropy was studied using a Monte Carlo approach in Nastran. The properties were then in a static structural response simulation of an irregularly-shape meteor (138-scale version of Asteroid Itokawa). Finally, an early plan was developed for doctoral research work at Georgia Tech. in the structural failure fragmentation of meteors.

  13. A Quantitative Study on the Relationship between Teachers' Technology Perceptions and Math Proficiency

    ERIC Educational Resources Information Center

    Wooldridge, Vernon William

    2009-01-01

    Increases in instructional technology investments in recent years have been discrepant with anticipated gains in math proficiency levels. Past researchers have attempted to explain the relationship between available educational technology and teacher-perceived benefits of technology-assisted instruction as a predictor of effective integration…

  14. DEVELOPMENT OF QUANTITATIVE STRUCTURE-ACTIVITY RELATIONSHIPS FOR PREDICTING BIODEGRADATION KINETICS

    EPA Science Inventory

    Results have been presented on the development of a structure-activity relationship for biodegradation using a group contribution approach. sing this approach, reported results of the kinetic rate constant agree within 20% with the predicted values. dditional compound studies are...

  15. The Relationship of Employee Status to Organizational Culture and Organizational Effectiveness: A Quantitative Analysis

    ERIC Educational Resources Information Center

    Deem, Jackie W.; DeLotell, Pam J.; Kelly, Kathryn

    2015-01-01

    Purpose: This study investigates the relationship between employment status (full time (FT)/part time (PT)), organizational culture and institutional effectiveness in higher education. The purpose of this paper is to answer the question, "Does the growing population of PT faculty preclude effective cultures from developing and, accordingly,…

  16. A Quantitative Review of the Relationship between Person-Organization Fit and Behavioral Outcomes

    ERIC Educational Resources Information Center

    Hoffman, Brian J.; Woehr, David J.

    2006-01-01

    This paper extends the meta-analysis of Verquer, Beehr, and Wagner by providing a meta-analytic review of the relationship between person-organization fit (PO fit) and behavioral criteria (job performance, organizational citizenship behaviors, and turnover). Results indicate that PO fit is weakly to moderately related to each of these outcome…

  17. Uncertainties have a Meaning: Quantitative Interpretation of the Relationship between Subsurface Flow and Geological Data Quality

    NASA Astrophysics Data System (ADS)

    Wellmann, J.; Regenauer-Lieb, K.; Western Australian Geothermal Centre of Excellence

    2011-12-01

    We present a new method to assess system-based measures to classify uncertainties in geological models and in subsurface flow fields. Information entropy is proposed to evaluate uncertainties in geological models, and thermal entropy production is proposed to analyze uncertainties related to hydrothermal flow. As these measures have a fundamental theoretical basis and are related to the internal state of the system, they can be interpreted quantitatively and, consequently, give uncertainties a meaning. Information entropy values are directly related to the state of uncertainty of a geological model. For a point within the model, information entropy is a measure of the minimum number of geological units that could occur at its location. If the information entropy is zero, only one unit is possible and no uncertainty exists. If the value is greater than zero, at least two units are probable. If it increases above 1, three units can occur. In general the measure provides a weight of probabiliy for different states. A strong point of the method is that it gives an entropy measure for the state of the entire model and therefore lends itself as a robust measure to quantitatively compare uncertainties in difference models. In a similar sense, the thermal entropy production provides a quantitative measure of the thermodynamic state of a hydrothermal system. When the entropy production is zero, the system must be in a conductive steady state for a closed system. If the entropy production is larger than zero, the system can be in a convective or transient conductive state. For higher values of entropy production, the convective units show higher complexities and, hence, uncertainty of the hydrothermal field increases. Moreover, the average model entropy production gives a measure of the convective vigour that can be expected in the system. This is directly related to the efficiency of heat transfer over the system. The measure is therefore not only useful for a

  18. Research of dose-effect relationship parameters of percutaneous microwave ablation for uterine leiomyomas--a quantitative study.

    PubMed

    Xia, Ma; Jing, Zhang; Zhi-yu, Han; Yu, Yang; Yan-li, Hao; Chang-tao, Xu; Rui-fang, Xu; Bing-song, Zhang; Bao-wei, Dong

    2014-01-01

    Eighty eight patients with 91 uterine leiomyomas who underwent ultrasound-guided percutaneous microwave ablation (PMWA) treatment were prospectively included in the study in order to study the dose-effect relationship parameters (DERP) of PMWA for uterine leiomyomas and its relationship with T2-weighted MR imaging (T2WI). Based on the signal intensity of T2WI, uterine leiomyomas were classified as hypointense, isointense, and hyperintense. During ablation, leiomyomas were treated with quantitative microwave ablation (QMWA) energy of 50 w × 300 s or 60 w × 300 s. After QMWA, contrast-enhanced ultrasound (CEUS) was performed to evaluate DERP. No matter under 50 w × 300 s or 60 w × 300 s, quantitative microwave ablation volume (QMAV) of hyperintense leiomyoma was smaller than that of hypointense and isointense leiomyoma (P<0.016). For hypointense and isointense leiomyoma, QMAV of 60 w × 300 s was larger than that of 50 w × 300 s (P<0.05). DERPs obtained by T2WI can be used to guide the treatment of uterine leiomyoma by PMWA. PMID:25267154

  19. Quantitative assessment of the relationships among ecological, morphological and aesthetic values in a river rehabilitation initiative.

    PubMed

    McCormick, Ashlee; Fisher, Karen; Brierley, Gary

    2015-04-15

    Promoting community support in rehabilitation efforts through incorporation of aesthetic considerations is an important component of environmental management. This research utilised a small-scale survey methodology to explore relationships among the ecological and morphological goals of scientists and the aesthetic goals of the public using the Twin Streams Catchment, Auckland, New Zealand, as a case study. Analyses using a linear model and a generalised linear mixed model showed statistically significant relationships between perceived naturalness of landscapes and their aesthetic ratings, and among ratings of perceived naturalness and ecological integrity and morphological condition. Expert measures of health and the aesthetic evaluations of the public were well aligned, indicating public preferences for landscapes of high ecological integrity with good morphological condition. Further analysis revealed participants used 'cues to care' to rate naturalness. This suggests that environmental education endeavours could further align values with these cues in efforts to enhance approaches to landscape sustainability. PMID:25660497

  20. The emotional coaching model: quantitative and qualitative research into relationships, communication and decisions in physical and sports rehabilitation.

    PubMed

    Respizzi, Stefano; Covelli, Elisabetta

    2015-01-01

    The emotional coaching model uses quantitative and qualitative elements to demonstrate some assumptions relevant to new methods of treatment in physical rehabilitation, considering emotional, cognitive and behavioral aspects in patients, whether or not they are sportsmen. Through quantitative tools (Tampa Kinesiophobia Scale, Emotional Interview Test, Previous Re-Injury Test, and reports on test scores) and qualitative tools (training contracts and relationships of emotional alliance or "contagion"), we investigate initial assumptions regarding: the presence of a cognitive and emotional mental state of impasse in patients at the beginning of the rehabilitation pathway; the curative value of the emotional alliance or "emotional contagion" relationship between healthcare provider and patient; the link between the patient's pathology and type of contact with his own body and emotions; analysis of the psychosocial variables for the prediction of possible cases of re-injury for patients who have undergone or are afraid to undergo reconstruction of the anterior cruciate ligament (ACL). Although this approach is still in the experimental stage, the scores of the administered tests show the possibility of integrating quantitative and qualitative tools to investigate and develop a patient's physical, mental and emotional resources during the course of his rehabilitation. Furthermore, it seems possible to identify many elements characterizing patients likely to undergo episodes of re-injury or to withdraw totally from sporting activity. In particular, such patients are competitive athletes, who fear or have previously undergone ACL reconstruction. The theories referred to (the transactional analysis theory, self-determination theory) and the tools used demonstrate the usefulness of continuing this research in order to build a shared coaching model treatment aimed at all patients, sportspeople or otherwise, which is not only physical but also emotional, cognitive and

  1. The emotional coaching model: quantitative and qualitative research into relationships, communication and decisions in physical and sports rehabilitation

    PubMed Central

    RESPIZZI, STEFANO; COVELLI, ELISABETTA

    2015-01-01

    The emotional coaching model uses quantitative and qualitative elements to demonstrate some assumptions relevant to new methods of treatment in physical rehabilitation, considering emotional, cognitive and behavioral aspects in patients, whether or not they are sportsmen. Through quantitative tools (Tampa Kinesiophobia Scale, Emotional Interview Test, Previous Re-Injury Test, and reports on test scores) and qualitative tools (training contracts and relationships of emotional alliance or “contagion”), we investigate initial assumptions regarding: the presence of a cognitive and emotional mental state of impasse in patients at the beginning of the rehabilitation pathway; the curative value of the emotional alliance or “emotional contagion” relationship between healthcare provider and patient; the link between the patient’s pathology and type of contact with his own body and emotions; analysis of the psychosocial variables for the prediction of possible cases of re-injury for patients who have undergone or are afraid to undergo reconstruction of the anterior cruciate ligament (ACL). Although this approach is still in the experimental stage, the scores of the administered tests show the possibility of integrating quantitative and qualitative tools to investigate and develop a patient’s physical, mental and emotional resources during the course of his rehabilitation. Furthermore, it seems possible to identify many elements characterizing patients likely to undergo episodes of re-injury or to withdraw totally from sporting activity. In particular, such patients are competitive athletes, who fear or have previously undergone ACL reconstruction. The theories referred to (the transactional analysis theory, self-determination theory) and the tools used demonstrate the usefulness of continuing this research in order to build a shared coaching model treatment aimed at all patients, sportspeople or otherwise, which is not only physical but also emotional, cognitive

  2. Quantitative relationship between silica exposure and lung cancer mortality in German uranium miners, 1946–2003

    PubMed Central

    Sogl, M; Taeger, D; Pallapies, D; Brüning, T; Dufey, F; Schnelzer, M; Straif, K; Walsh, L; Kreuzer, M

    2012-01-01

    Background: In 1996 and 2009, the International Agency for Research on Cancer classified silica as carcinogenic to humans. The exposure–response relationship between silica and lung cancer risk, however, is still debated. Data from the German uranium miner cohort study were used to further investigate this relationship. Methods: The cohort includes 58 677 workers with individual information on occupational exposure to crystalline silica in mg m−3-years and the potential confounders radon and arsenic based on a detailed job-exposure matrix. In the follow-up period 1946–2003, 2995 miners died from lung cancer. Internal Poisson regression with stratification by age and calendar year was used to estimate the excess relative risk (ERR) per dust-year. Several models including linear, linear quadratic and spline functions were applied. Detailed adjustment for cumulative radon and arsenic exposure was performed. Results: A piecewise linear spline function with a knot at 10 mg m−3-years provided the best model fit. After full adjustment for radon and arsenic no increase in risk <10 mg m−3-years was observed. Fixing the parameter estimate of the ERR in this range at 0 provided the best model fit with an ERR of 0.061 (95% confidence interval: 0.039, 0.083) >10 mg m−3-years. Conclusion: The study confirms a positive exposure–response relationship between silica and lung cancer, particularly for high exposures. PMID:22929885

  3. Structure-Property Relationship in Metal Carbides and Bimetallic Alloys

    SciTech Connect

    Chen, Jingguan

    2014-03-04

    The primary objective of our DOE/BES sponsored research is to use carbide and bimetallic catalysts as model systems to demonstrate the feasibility of tuning the catalytic activity, selectivity and stability. Our efforts involve three parallel approaches, with the aim at studying single crystal model surfaces and bridging the “materials gap” and “pressure gap” between fundamental surface science studies and real world catalysis. The utilization of the three parallel approaches has led to the discovery of many intriguing catalytic properties of carbide and bimetallic surfaces and catalysts. During the past funding period we have utilized these combined research approaches to explore the possibility of predicting and verifying bimetallic and carbide combinations with enhanced catalytic activity, selectivity and stability.

  4. Structure-Property Relationships in Oxides Containing Tellurium

    NASA Astrophysics Data System (ADS)

    Siritanon, Theeranun

    Oxides of post-transition metals often show unique structures and properties due to the presence of lone pair electrons and the diffused s orbitals. The present work focuses on synthesis and characterizations of oxides containing Te, a heavy post transition metal. New series of pyrochlore oxides of the formula Cs(M,Te)2O 6 (M = Al, Ga, Cr, Fe, Co, In, Ho, Lu, Yb, Er, Ge, Rh, Ti, Zn, Ni, and Mg) have been prepared. The samples were highly colored (ranging from black to dark green) indicating a possible mixed valency for Te with appreciable charge transfer between them in the octahedral sites. Electronic conductivity was observed in some phases and could be as high as 2S/cm (M=Ge). Seebeck coefficients of conducting samples show negative values which suggest that electrons are the major charge carriers. Temperature dependence of conductivity indicates that the samples are semiconductors with, in some cases, degenerate semiconducting behavior. Detailed studies on the conduction mechanism indicate the mixed valency of tellurium which leads to semiconducting behavior and the color of the compounds. Systematic studies of cesium tellurate with CsTe2O6-x where x = 0, 0.15, 0.25, 1.5 have been investigated. On heating at slightly above 600ºC, CsTe2O6 loses oxygen resulting in cubic structure with disordered Te4+/Te6+ and oxygen vacancies. Two novel phases of CsTe2O6-x were prepared with orthorhombic structure. The first phase with x value of about 0.2-0.3 crystallizes in Pnma symmetry. At higher values of x, a new compound was discovered with a structure related to Rb4Te 8O23. Optical properties of the compounds are consistent with their colors. CsTe2O6 belongs to class II mixed valency according to Robin and Day classification. However, structures and properties of CsTe 2O6-x phases indicate that they are class I mixed valence compounds. Series of compounds with formula CsTe2-xWxO 6 with x=0.2-0.5 have been made which can be considered as solid solution of CsTe2O6 and CsTe0.5W1.5O 6. Although the two end members adopt rhombohedral and trigonal structure, these solid solution phases crystallize in cubic defect pyrochlore structure with W6+, Te6+, and Te4+ randomly occupying 16c octahedral site. The compounds show no electronic conductivity at room temperature. Novel cubic pyrochlore with the formula (CdBi)(MTe)O7, M= Al, Cr, Ga, In, Fe, Mn, and Sc were synthesized by solid state reaction using oxides of the constituent elements. Magnetic properties analyses show paramagnetism in M=Cr and Mn but antiferromagnetism with short-range correlation in M= Fe phase. All compositions are insulating. Dielectric measurements show relatively low dielectric constants which are independent of temperature and frequency. Metallic Tl2TeO6 and insulating In2TeO 6 are both known to crystallize in the Na2SiF6-type structure. We have now prepared a complete Tl2-xInxTeO6 series in a search for a compositionally controlled metal-insulator transition that might be expected if a complete solid solution can be obtained. Unit cell edges and volume vary monotonically with no indication of miscibility gap. The metal-insulator transition occurs at an x value of about 1.4, which can be rationalized on a percolation model. No superconductivity could be detected down to 5K. Rh2MO6, M = Mo, W, and Te were synthesized by solid state reaction. Electronic properties as well as thermoelectric properties were investigated and discussed. The compounds crystallize in rutile-related structure and all show relatively high electronic conductivities with Rh 2TeO6 showing the highest electronic conductivity (˜500 S/cm at room temperature) despite localized electrons in Rh3+ and Te6+. Measurable magnetic moments also indicate valence degeneracy between Rh and the M cation. The measured Seebeck coefficients are relatively low and positive indicating hole-type conduction.

  5. Structure Property Relationships in Imidazole-based Deep Eutectic Mixtures

    NASA Astrophysics Data System (ADS)

    Terheggen, Logan; Cosby, Tyler; Sangoro, Joshua

    2015-03-01

    Deep eutectic mixtures of levulinic acid with a systematic series of imidazoles are measured by broadband dielectric spectroscopy, differential scanning calorimetry, and Fourier transform infrared spectroscopy to investigate the impact of steric interactions on charge transport and structural dynamics. An enhancement of dc conductivity is found in each of the imidazoles upon the addition of levulinic acid. However, the extent of increase is dependent upon the alkyl substitution on the imidazole ring. These results highlight the importance of molecular structure on hydrogen bonding and charge transport in deep eutectic mixtures.

  6. Cement-aggregate compatibility and structure property relationships including modelling

    SciTech Connect

    Jennings, H.M.; Xi, Y.

    1993-07-15

    The role of aggregate, and its interface with cement paste, is discussed with a view toward establishing models that relate structure to properties. Both short (nm) and long (mm) range structure must be considered. The short range structure of the interface depends not only on the physical distribution of the various phases, but also on moisture content and reactivity of aggregate. Changes that occur on drying, i.e. shrinkage, may alter the structure which, in turn, feeds back to alter further drying and shrinkage. The interaction is dynamic, even without further hydration of cement paste, and the dynamic characteristic must be considered in order to fully understand and model its contribution to properties. Microstructure and properties are two subjects which have been pursued somewhat separately. This review discusses both disciplines with a view toward finding common research goals in the future. Finally, comment is made on possible chemical reactions which may occur between aggregate and cement paste.

  7. Synthesis and Structure - Property Relationships for Regular Multigraft Copolymers

    SciTech Connect

    Mays, Jimmy; Uhrig, David; Gido, Samuel; Zhu, Yuqing; Weidisch, Roland; Iatrou, Hermis; Hadjichristidis, Nikos; Hong, Kunlun; Beyer, Frederick; Lach, Ralph

    2004-01-01

    Multigraft copolymers with polyisoprene backbones and polystyrene branches, having multiple regularly spaced branch points, were synthesized by anionic polymerization high vacuum techniques and controlled chlorosilane linking chemistry. The functionality of the branch points (1, 2 and 4) can be controlled, through the choice of chlorosilane linking agent. The morphologies of the various graft copolymers were investigated by transmission electron microscopy and X-ray scattering. It was concluded that the morphology of these complex architectures is governed by the behavior of the corresponding miktoarm star copolymer associated with each branch point (constituting block copolymer), which follows Milner's theoretical treatment for miktoarm stars. By comparing samples having the same molecular weight backbone and branches but different number of branches it was found that the extent of long range order decreases with increasing number of branch points. The stress-strain properties in tension were investigated for some of these multigraft copolymers. For certain compositions thermoplastic elastomer (TPE) behavior was observed, and in many instances the elongation at break was much higher (2-3X) than that of conventional triblock TPEs.

  8. Structure-Property Relationships in Polyolefin Block Copolymers

    NASA Astrophysics Data System (ADS)

    Mansour, Ameara Salah

    Poly(cyclohexylethylene) (PCHE for a homopolymer or C in a block copolymer) is created by hydrogenating polystyrene, and this polymer exhibits interesting properties, such as a high glass transition temperature (147 °C), high flexural modulus (2.8 GPa), low stress optical coefficient (-0.2 * 10-9 Pa-1), and low cost. However, the inherently brittle nature of PCHE prevents it from being used in applications that simultaneously require high modulus, ductility, thermal stability, and optical clarity. Previous research has shown that incorporating PCHE into a block copolymer with rubbery poly(ethylene-alt-propylene) (P) or poly(ethylethylene) (EE) or semicrystalline polyethylene (E) results in a tough material. In some cases, applications also require specific mechanical or optical properties. In order to tune these properties, this research examined tuning crystallinity using two methods: (1) by controlling the microstructure of the soft block by synthesizing a random copolymer of E and EE, and (2) by blending high C content pentablock copolymers with semicrystalline and rubbery minority components. In the first study, diblock copolymers of C(EcoEE) also were used to understand how the microstructure of the random copolymer affects the thermodynamics of the system. In the second study, CECEC and CPCPC, designed to form the same morphology (hexagonally packed cylinders with glassy C matrices), and have similar order-to-disorder transition temperatures and domain spacings, were blended together. Isothermal crystallization experiments were used to determine how the confining E and P in one domain affects the crystallization process. The effect of architecture, the state of the minority component, and the percent crystallinity on the mechanical properties of high glass content materials was also examined. These results were compared to the mechanical properties of homopolymer PCHE, polystyrene, and polycarbonate. The processing conditions needed to create smooth films of CECEC with a high fraction of C, which could be used in optical experiments, were determined.

  9. Structure properties relationship in electrospun thermoset butyl rubber

    NASA Astrophysics Data System (ADS)

    Viriyabanthorn, Nantiya

    Development of breathable elastomeric membranes based upon butyl rubber (IIR) compounds was investigated. These semi-permeable membranes were produced by electrospinning the compounded butyl rubber under appropriate conditions. They were designed to be selectively permeable. Specifically, these elastomeric membranes allowed moisture vapor transport, while maintaining a barrier against liquid water. Additionally, the conductive nature of carbon black in the compounds was shown to allow greater control over membrane thickness than generally observed in electrospun fabrics. Data were presented to show that the excellent chemical resistance of butyl rubber to organic solvents and toxic agents was maintained despite the porous nature of the membranes. Air flow resistance could also be adjusted as functions of processing conditions which related to fiber diameter and porosity of the membrane. Mechanical properties, in addition to various transport properties, are compared to a butyl rubber baseline. The moisture vapor transport properties are compared to expanded PTFE films. The results demonstrate the effectiveness of thermoset elastomeric membranes for producing flexible, selectively permeable barriers. Moreover, It also shows the capability to produce nonwoven materials for applications requiring high elongation (stretch) and porosity. In most elastomer formulations, carbon black is used as filler because of its reinforcing properties. The addition of carbon was also found to be important in the electrospinning of butyl rubber. Carbon black typically results in improved mechanical properties for rubber compounds, however, its conductive properties can also play a role in the resulting fiber structure during the electrospinning process. Carbon black loadings were varied from 0, 25, 50, and 75 parts per hundred rubber (phr). Increased carbon black loading resulted in a larger process window and reduced density and bead formation. Tensile modulus (corrected for changes in density) increased with increasing carbon black loading. Elongation of butyl rubber mats decreased at higher carbon black levels, however, more than 1000% was observed in all cases.

  10. Structure-Property Relationships of Architectural Coatings by Neutron Methods

    NASA Astrophysics Data System (ADS)

    Nakatani, Alan

    2015-03-01

    Architectural coatings formulations are multi-component mixtures containing latex polymer binder, pigment, rheology modifiers, surfactants, and colorants. In order to achieve the desired flow properties for these formulations, measures of the underlying structure of the components as a function of shear rate and the impact of formulation variables on the structure is necessary. We have conducted detailed measurements to understand the evolution under shear of local microstructure and larger scale mesostructure in model architectural coatings formulations by small angle neutron scattering (SANS) and ultra small angle neutron scattering (USANS), respectively. The SANS results show an adsorbed layer of rheology modifier molecules exist on the surface of the latex particles. However, the additional hydrodynamic volume occupied by the adsorbed surface layer is insufficient to account for the observed viscosity by standard hard sphere suspension models (Krieger-Dougherty). The USANS results show the presence of latex aggregates, which are fractal in nature. These fractal aggregates are the primary structures responsible for coatings formulation viscosity. Based on these results, a new model for the viscosity of coatings formulations has been developed, which is capable of reproducing the observed viscosity behavior.

  11. A proposal for a multivariate quantitative approach to infer karyological relationships among taxa.

    PubMed

    Peruzzi, Lorenzo; Altınordu, Fahim

    2014-01-01

    Until now, basic karyological parameters have been used in different ways by researchers to infer karyological relationships among organisms. In the present study, we propose a standardized approach to this aim, integrating six different, not redundant, parameters in a multivariate PCoA analysis. These parameters are chromosome number, basic chromosome number, total haploid chromosome length, MCA (Mean Centromeric Asymmetry), CVCL (Coefficient of Variation of Chromosome Length) and CVCI (Coefficient of Variation of Centromeric Index). The method is exemplified with the application to several plant taxa, and its significance and limits are discussed in the light of current phylogenetic knowledge of these groups. PMID:25610547

  12. A proposal for a multivariate quantitative approach to infer karyological relationships among taxa

    PubMed Central

    Peruzzi, Lorenzo; Altınordu, Fahim

    2014-01-01

    Abstract Until now, basic karyological parameters have been used in different ways by researchers to infer karyological relationships among organisms. In the present study, we propose a standardized approach to this aim, integrating six different, not redundant, parameters in a multivariate PCoA analysis. These parameters are chromosome number, basic chromosome number, total haploid chromosome length, MCA (Mean Centromeric Asymmetry), CVCL (Coefficient of Variation of Chromosome Length) and CVCI (Coefficient of Variation of Centromeric Index). The method is exemplified with the application to several plant taxa, and its significance and limits are discussed in the light of current phylogenetic knowledge of these groups. PMID:25610547

  13. Composite scores for executive function items: demographic heterogeneity and relationships with quantitative magnetic resonance imaging.

    PubMed

    Crane, Paul K; Narasimhalu, Kaavya; Gibbons, Laura E; Pedraza, Otto; Mehta, Kala M; Tang, Yuxiao; Manly, Jennifer J; Reed, Bruce R; Mungas, Dan M

    2008-09-01

    Accurate neuropsychological assessment of older individuals from heterogeneous backgrounds is a major challenge. Education, ethnicity, language, and age are associated with scale level differences in test scores, but item level bias might contribute to these differences. We evaluated several strategies for dealing with item and scale level demographic influences on a measure of executive abilities defined by working memory and fluency tasks. We determined the impact of differential item functioning (DIF). We compared composite scoring strategies on the basis of their relationships with volumetric magnetic resonance imaging (MRI) measures of brain structure. Participants were 791 Hispanic, white, and African American older adults. DIF had a salient impact on test scores for 9% of the sample. MRI data were available on a subset of 153 participants. Validity in comparison with structural MRI was higher after scale level adjustment for education, ethnicity/language, and gender, but item level adjustment did not have a major impact on validity. Age adjustment at the scale level had a negative impact on relationships with MRI, most likely because age adjustment removes variance related to age-associated diseases. PMID:18764970

  14. Structural Properties of the Native Ligamentum Teres

    PubMed Central

    Philippon, Marc J.; Rasmussen, Matthew T.; Turnbull, Travis Lee; Trindade, Christiano A.C.; Hamming, Mark G.; Ellman, Michael B.; Harris, Matthew; LaPrade, Robert F.; Wijdicks, Coen A.

    2014-01-01

    Background: A majority of studies investigating the role of the ligamentum teres (LT) have focused primarily on anatomical and histological descriptions. To date, however, the structural properties of the LT have yet to be fully elucidated. Purpose: To investigate the structural properties of the native LT in a human cadaveric model. Study Design: Descriptive laboratory study. Methods: A total of 12 human cadaveric hemipelvises (mean age, 53.6 years; range, 34-63 years) were dissected free of all extra-articular soft tissues to isolate the LT and its acetabular and femoral attachments. A dynamic tensile testing machine distracted each femur in line with the fibers of the LT at a displacement-controlled rate of 0.5 mm/s. The anatomic dimensions, structural properties, and modes of failure were recorded. Results: The LT achieved a mean yield load of 75 N and ultimate failure load of 204 N. The LT had mean lengths of 38.0 and 53.0 mm at its yield and failure points, respectively. The most common (75% of specimens) mechanism of failure was tearing at the fovea capitis. On average, the LT had a linear stiffness of 16 N/mm and elastic modulus of 9.24 MPa. The mean initial length and cross-sectional area were 32 mm and 59 mm2, respectively. Conclusion: The human LT had a mean ultimate failure load of 204 N. Therefore, the results of this investigation, combined with recent biomechanical and outcomes studies, suggest that special consideration should be given to preserving the structural and corresponding biomechanical integrity of the LT during surgical intervention. Clinical Relevance: The LT may be more important as a static stabilizer of the hip joint than previously recognized. Further studies are recommended to investigate the appropriate indications to perform surgical repair or reconstruction of the LT for preservation of hip stability and function. PMID:26535290

  15. Earthquakes Versus Surface Deformation: Qualitative and Quantitative Relationships From The Aegean

    NASA Astrophysics Data System (ADS)

    Pavlides, S.; Caputo, R.

    Historical seismicity of the Aegean Region has been revised in order to associate major earthquakes to specific seismogenic structures. Only earthquakes associated to normal faulting have been considered. All available historical and seismotectonic data relative to co-seismic surface faulting have been collected in order to evaluate the surface rup- ture length (SRL) and the maximum displacement (MD). In order to perform Seismic Hazard analyses, empirical relationships between these parameters and the magnitude have been inferred and the best fitting regression functions have been calculated. Both co-seismic fault rupture lengths and maximum displacements show a logarithmic re- lationships, but our data from the Aegean Region have systematically lower values than the same parameters world-wide though they are similar to those of the East- ern Mediterranean-Middle East region. The upper envelopes of our diagrams (SRL vs Mw and MD vs Mw) have been also estimated and discussed, because they give useful information of the wort-case scenarios; these curces will be also discussed. Further- more, geological and morphological criteria have been used to recognise the tectonic structures along which historical earthquakes occurred in order to define the geolog- ical fault length (GFL). Accordingly, the SRL/GFL ratio seems to have a bimodal distribution with a major peak about 0.8-1.0, indicating that several earthquakes break through almost the entire geological fault length, and a second peak around 0.5, re- lated to the possible segmentation of these major neotectonic faults. In contrast, no relationships can be depicted between the SRL/GFL ratio and the magnitude of the corresponding events.

  16. Studying the explanatory capacity of artificial neural networks for understanding environmental chemical quantitative structure-activity relationship models.

    PubMed

    Yang, Lei; Wang, Peng; Jiang, Yilin; Chen, Jian

    2005-01-01

    Although artificial neural networks (ANNs) have been shown to exhibit superior predictive power in the study of quantitative structure-activity relationships (QSARs), they have also been labeled a "black box" because they provide little explanatory insight into the relative influence of the independent variables in the predictive process so that little information on how and why compounds work can be obtained. Here, we have turned our interests to their explanatory capacities; therefore, a method was proposed for assessing the relative importance of variables indicating molecular structure, on the basis of axon connection weights and partial derivatives of the ANN output with respect to its input, which can identify variables that significantly contribute to network predictions, and providing a variable selection method for ANNs. We show that, by extending this approach to ANNs, the "black box" mechanics of ANNs can be greatly illuminated, thereby making it very useful in understanding environmental chemical QSAR models. PMID:16309287

  17. Semisynthesis and quantitative structure-activity relationship (QSAR) study of some cholesterol-based hydrazone derivatives as insecticidal agents.

    PubMed

    Yang, Chun; Shao, Yonghua; Zhi, Xiaoyan; Huan, Qu; Yu, Xiang; Yao, Xiaojun; Xu, Hui

    2013-09-01

    In continuation of our program aimed at the discovery and development of natural-product-based insecticidal agents, four series of novel cholesterol-based hydrazone derivatives were synthesized, and their insecticidal activity was tested against the pre-third-instar larvae of oriental armyworm, Mythimna separata (Walker) in vivo at 1mg/mL. All the derivatives showed the better insecticidal activity than their precursor cholesterol. Quantitative structure-activity relationship (QSAR) model demonstrated that six descriptors such as RDF085v, Mor06u, Mor11u, Dv, HATS0v and H-046, are likely to influence the insecticidal activity of these compounds. Among them, two important ones are the Mor06u and RDF085v. PMID:23891182

  18. Estimating the persistence of organic contaminants in indirect potable reuse systems using quantitative structure activity relationship (QSAR).

    PubMed

    Lim, Seung Joo; Fox, Peter

    2012-09-01

    Predictions from the quantitative structure activity relationship (QSAR) model EPI Suite were modified to estimate the persistence of organic contaminants in indirect potable reuse systems. The modified prediction included the effects of sorption, biodegradation, and oxidation that may occur during sub-surface transport. A retardation factor was used to simulate the mobility of adsorbed compounds during sub-surface transport to a recovery well. A set of compounds with measured persistent properties during sub-surface transport was used to validate the results of the modifications to the predictions of EPI Suite. A comparison of the predicted values and measured values was done and the residual sum of the squares showed the importance of including oxidation and sorption. Sorption was the most important factor to include in predicting the fates of organic chemicals in the sub-surface environment. PMID:22766422

  19. Structural properties of autoclaved aerated concrete masonry

    SciTech Connect

    Matthys, J.H.; Nelson, R.L.

    1999-07-01

    Autoclaved aerated concrete masonry units are manufactured from portland cement, quartz sand, water, lime, gypsum and a gas forming agent. The units are steam cured under pressure in an autoclave transforming the material into a hard calcium silicate. The autoclaved aerated concrete masonry units are large-size solid rectangular prisms which are laid using thin-bed mortar layers into masonry assemblages. The system and product are not new--patented in 1924 by Swedish architect Johan Eriksson. Over a period of 60 years this product has been used in all areas of residential and industrial construction and in virtually all climates. However, the principal locations of application have been generally outside the US Little information in the US is available on the structural properties of this product. Due to the interest in use of this product in the construction industry and the construction of production plants in the US, the Construction Research Center at the University of Texas at Arlington and Robert L. Nelson & Associates conducted a series of tests to determine some of the basic structural properties of this product. This paper presents the findings of those investigations.

  20. Effective structural properties in polycrystalline graphene

    NASA Astrophysics Data System (ADS)

    Hossain, Zubaer

    This talk will discuss effective structural properties in polycrystalline graphene under the presence of atomic scale heterogeneity. Polycrystallinity is ubiquitous in solids, but theories describing their effective behavior remain limited, particularly when heterogeneity is present in the form of nonuniform deformation or composition. Over the decades, exploration of the effective transport and strength properties of heterogeneous systems has been carried out mostly with random distribution of grains or regular periodic structures under various approximations, in translating the underlying physics into a single representative volume element. Although heterogeneity can play a critical role in modulating the basic behavior of low-dimensional materials, it is difficult to capture the local characteristics accurately by these approximations. Taking polycrystalline graphene as an example material, we study the effective structural properties (such as Young's Modulus, Poisson's ratio and Toughness) by using a combination of density functional theory and molecular dynamic simulations. We identify the key mechanisms that govern their effective behavior and exploit the understanding to engineer the behavior by doping with a carefully selected choice of chemical elements.

  1. Structural properties of small rhodium clusters

    SciTech Connect

    Soon, Yee Yeen; Yoon, Tiem Leong; Lim, Thong Leng

    2015-04-24

    We report a systematic study of the structural properties of rhodium clusters at the atomistic level. A novel global-minimum search algorithm, known as parallel tempering multicanonical basin hopping plus genetic algorithm (PTMBHGA), is used to obtain the geometrical structures with lowest minima at the semi-empirical level where Gupta potential is used to describe the atomic interaction among the rhodium atoms. These structures are then re-optimized at the density functional theory (DFT) level with exchange-correlation energy approximated by Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA). The structures are optimized for different spin multiplicities. The ones with lowest energies will be taken as ground-state structures. In most cases, we observe only minor changes in the geometry and bond length of the clusters as a result of DFT-level re-optimization. Only in some limited cases, the initial geometries obtained from the PTMBHGA are modified by the re-optimization. The variation of structural properties, such as ground-state geometry, symmetry and binding energy, with respect to the cluster size is studied and agreed well with other results available in the literature.

  2. Quantitative structure-activation barrier relationship modeling for Diels-Alder ligations utilizing quantum chemical structural descriptors

    PubMed Central

    2013-01-01

    Background In the present study, we show the correlation of quantum chemical structural descriptors with the activation barriers of the Diels-Alder ligations. A set of 72 non-catalysed Diels-Alder reactions were subjected to quantitative structure-activation barrier relationship (QSABR) under the framework of theoretical quantum chemical descriptors calculated solely from the structures of diene and dienophile reactants. Experimental activation barrier data were obtained from literature. Descriptors were computed using Hartree-Fock theory using 6-31G(d) basis set as implemented in Gaussian 09 software. Results Variable selection and model development were carried out by stepwise multiple linear regression methodology. Predictive performance of the quantitative structure-activation barrier relationship (QSABR) model was assessed by training and test set concept and by calculating leave-one-out cross-validated Q2 and predictive R2 values. The QSABR model can explain and predict 86.5% and 80% of the variances, respectively, in the activation energy barrier training data. Alternatively, a neural network model based on back propagation of errors was developed to assess the nonlinearity of the sought correlations between theoretical descriptors and experimental reaction barriers. Conclusions A reasonable predictability for the activation barrier of the test set reactions was obtained, which enabled an exploration and interpretation of the significant variables responsible for Diels-Alder interaction between dienes and dienophiles. Thus, studies in the direction of QSABR modelling that provide efficient and fast prediction of activation barriers of the Diels-Alder reactions turn out to be a meaningful alternative to transition state theory based computation. PMID:24171724

  3. Quantitative relationship between capsular content and killing of K1-encapsulated Escherichia coli.

    PubMed Central

    Vermeulen, C; Cross, A; Byrne, W R; Zollinger, W

    1988-01-01

    Since there are conflicting reports in the literature on a possible relationship between the K1 capsular polysaccharide (CP) content of Escherichia coli and its susceptibility to killing, we reexamined this issue in a strain that had a smooth lipopolysaccharide (LPS) phenotype (E. coli O18:K1:H7 Bort) and in a strain with a deep rough LPS phenotype (E412, spontaneously agglutinable: K1:H-). When cell-associated K1 capsular content was greater than 90 micrograms of K1 polysaccharide per 10(10) CFU, neither strain was lysed by 20% normal human serum. In contrast, at equivalent but lower levels of K1 CP content, E412 but not strain Bort was lysed by normal human serum. Thus, LPS phenotype is an additional surface determinant that affects bacterial susceptibility to killing. Organisms obtained from very early log phase, when cell-associated K1 CP is greatest, were significantly more virulent for mice than were bacteria harvested in stationary phase, when cell-associated K1 polysaccharide is lowest. We conclude that (i) there is a threshold level of K1 CP needed to confer protection from lysis by serum, and this is usually exceeded under standard growth conditions; (ii) at a given level of K1 CP the LPS phenotype is an important determinant of bacterial killing; and (iii) the loss of capsule at low pH may be an additional mechanism by which hosts defend against invasive infection by K1-encapsulated E. coli. Images PMID:3047064

  4. Chemical composition and quantitative relationship between meteorological condition and fine particles in Beijing.

    PubMed

    Wang, Jing-Li; Zhang, Yuan-Hang; Shao, Min; Liu, Xu-Lin; Zeng, Li-Min; Cheng, Cong-Lan; Xu, Xiao-Feng

    2004-01-01

    The recent year's monitor results of Beijing indicated that the pollution level of fine particles PM2.5 showed an increasing trend. To understand pollution characteristics of PM2.5 and its relationship with the meteorological conditions in Beijing, a one-year monitoring of PM2.5 mass concentration and correspondent meteorological parameters was performed in Beijing in 2001. The PM2.5 levels in Beijing were very high, the annual average PM2.5 concentration in 2001 was 7 times of the National Ambient Air Quality Standards proposed by US EPA. The major chemical compositions were organics, sulfate, crustals and nitrate. It was found that the mass concentrations of PM2.5 were influenced by meteorological conditions. The correlation between the mass concentrations of PM2.5 and the relative humidity was found. And the correlation became closer at higher relative humidity. And the mass concentrations of PM2.5 were negtive-correlated to wind speeds, but the correlation between the mass concentration of PM2.5 and wind speed was not good at stronger wind. PMID:15559829

  5. Quantitative structure-activity relationships for skin sensitization potential of urushiol analogues.

    PubMed

    Roberts, D W; Benezra, C

    1993-08-01

    The relative alkylation index (RAI), a theoretically derived parameter intended to quantify the relative extent of carrier haptenation resulting from a given dose of a given sensitizer, has previously been successfully applied to the analysis of relative sensitization potential and dose-response data for a variety of contact allergens which are directly electrophilic. Here the RAI concept is applied to analysis of data on compounds related to urushiol (i.e., 3-substituted catechols), the naturally occurring mixture of allergens responsible for contact allergy to poison ivy and poison oak. These allergens are believed to act as pro-electrophiles, being oxidized to electrophilic orthoquinones in vivo. It is found that the various types of urushiol derivatives fit the same sort of RAI-sensitization relationships as expected theoretically and as found previously with direct acting electrophiles. There is evidence that in many cases, the test conditions were such that overload effects, whereby the degree of sensitization induced decreases with increasing carrier haptenation, applied. It is also concluded that the question as to the relative sensitization potencies of the naturally occurring urushiols remains open. The commonly held view that with these materials, sensitization potential increases with increasing unsaturation in the 3-hydrocarbyl chain of the 3-hydrocarbyl catechols, is based on evidence that is capable of alternative interpretation. PMID:8365181

  6. The Relationship between Serum Vitamin D Levels and Spinal Fusion Success: A Quantitative Analysis

    PubMed Central

    Metzger, Melodie F.; Kanim, Linda E.; Zhao, Li; Robinson, Samuel T.; Delamarter, Rick B.

    2015-01-01

    Study Design An in vivo dosing study of vitamin D in a rat posterolateral spinal fusion model with autogenous bone grafting. Rats randomized to four levels of Vitamin D adjusted rat chow, longitudinal serum validation, surgeons/observers blinded to dietary conditions, and rats followed prospectively for fusion endpoint. Objective To assess the impact of dietary and serum levels of Vitamin D on fusion success, consolidation of fusion mass, and biomechanical stiffness after posterolateral spinal fusion procedure. Summary of Background Data Metabolic risk factors, including vitamin D insufficiency, are often overlooked by spine surgeons. Currently there are no published data on the causal effect of insufficient or deficient vitamin D levels on the success of establishing solid bony union after a spinal fusion procedure. Methods 50 rats were randomized to four experimentally controlled rat chow diets: normal control, vitamin D-deficient, vitamin-D insufficient, and a non-toxic high dose of vitamin D, four weeks prior to surgery and maintained post-surgery until sacrifice. Serum levels of 25(OH)D were determined at surgery and sacrifice using radioimmunoassay. Posterolateral fusion surgery with tail autograft was performed. Rats were sacrificed 12 weeks post-operatively and fusion was evaluated via manual palpation, high resolution radiographs, μCT, and biomechanical testing. Results Serum 25(OH)D and calcium levels were significantly correlated with vitamin-D adjusted chow (p<0.001). There was a dose dependent relationship between vitamin D adjusted chow and manual palpation fusion with greatest differences found in measures of radiographic density between high and deficient vitamin D (p<0.05). Adequate levels of vitamin D (high and normal control) yielded stiffer fusion than inadequate levels (insufficient and deficient) (p<0.05). Conclusions Manual palpation fusion rates increased with supplementation of dietary vitamin D. Biomechanical stiffness, bone volume and

  7. Quantitative and temporal relationships of egg production and sound production by black drum Pogonias cromis.

    PubMed

    Locascio, J V; Burghart, S; Mann, D A

    2012-09-01

    The timing and levels of black drum Pogonias cromis sound production and egg production were compared in an estuarine canal basin of Cape Coral in south-west Florida. Surface plankton samples were collected hourly from 1800 to 0400 on two consecutive nights while continuous acoustic recordings were made simultaneously at five locations in the canal basin. Five pairs of nights were sampled during a part of the spawning season from late January to early April 2006. Pogonias cromis sound production and egg production occurred on all evenings that samples were collected; however, both the timing and levels of sound production were negatively associated with those of egg production. Egg production estimates ranged from a low of 4·8 eggs m(-3) in February to a high of 2889·2 eggs m(-3) in April. Conversely, maximum nightly sound pressure levels (SPL) ranged from a low of 89·5 dB in April to a high of 131·9 dB (re: 1 µPa) in February. The temporal centre of sound production was relatively stable among all nights sampled but spawning occurred earlier in the day as the season progressed and exhibited a strong, positive association with increased water temperature. The negative relationship between the levels of sound production and egg production was unexpected given the usefulness of sound production as a proxy for reproduction on a seasonal basis and may possibly be explained by differences in the spawning potential of the female population in the study area on nights sampled. Egg mortality rates increased throughout the season and were positively associated with densities of hydrozoans and ctenophores. PMID:22957862

  8. A NON-LINEAR STRUCTURE-PROPERTY MODEL FOR OCTANOL-WATER PARTITION COEFFICIENT

    PubMed Central

    Yerramsetty, Krishna M.; Neely, Brian J.; Gasem, Khaled A. M.

    2012-01-01

    Octanol-water partition coefficient (Kow) is an important thermodynamic property used to characterize the partitioning of solutes between an aqueous and organic phase and has importance in such areas as pharmacology, pharmacokinetics, pharmacodynamics, chemical production and environmental toxicology. We present a non-linear quantitative structure-property relationship model for determining Kow values of new molecules in silico. A total of 823 descriptors were generated for 11,308 molecules whose Kow values are reported in the PhysProp dataset by Syracuse Research. Optimum network architecture and its associated inputs were identified using a wrapper-based feature selection algorithm that combines differential evolution and artificial neural networks. A network architecture of 50-33-35-1 resulted in the least root-mean squared error (RMSE) in the training set. Further, to improve on single-network predictions, a neural network ensemble was developed by combining five networks that have the same architecture and inputs but differ in layer weights. The ensemble predicted the Kow values with RMSE of 0.28 and 0.38 for the training set and internal validation set, respectively. The ensemble performed reasonably well on an external dataset when compared with other popular Kow models in the literature. PMID:23185102

  9. Structure-guided unravelling: Phenolic hydroxyls contribute to reduction of acrylamide using multiplex quantitative structure-activity relationship modelling.

    PubMed

    Zhang, Yu; Huang, Mengmeng; Wang, Qiao; Cheng, Jun

    2016-05-15

    We reported a structure-activity relationship study on unravelling phenolic hydroxyls instead of alcoholic hydroxyls contribute to the reduction of acrylamide formation by flavonoids. The dose-dependent study shows a close correlation between the number of phenolic hydroxyls of flavonoids and their reduction effects. In view of positions of hydroxyls, the 3',4'(ortho)-dihydroxyls in B cycle, 3-hydroxyl or hydroxyls of 3-gallate in C cycle, and 5,7(meta)-dihydroxyls in A cycle of flavonoid structures play an important role in the reduction of acrylamide. Flavone C-glycosides are more effective at reducing the formation of acrylamide than flavone O-glycosides when sharing the same aglycone. The current multiplex quantitative structure-activity relationship (QSAR) equations effectively predict the inhibitory rates of acrylamide using selected chemometric parameters (R(2): 0.835-0.938). This pioneer study opens a broad understanding on the chemoprevention of acrylamide contaminants on a structural basis. PMID:26776000

  10. Inverse relationship between photon flux densities and nanotesla magnetic fields over cell aggregates: Quantitative evidence for energetic conservation

    PubMed Central

    Persinger, Michael A.; Dotta, Blake T.; Karbowski, Lukasz M.; Murugan, Nirosha J.

    2015-01-01

    The quantitative relationship between local changes in magnetic fields and photon emissions within ∼2 mm of aggregates of 105–106 cells was explored experimentally. The vertical component of the earth’s magnetic field as measured by different magnetometers was ∼15 nT higher when plates of cells removed from incubation were measured compared to plates containing only medium. Additional experiments indicated an inverse relationship over the first ∼45 min between changes in photon counts (∼10−12 W·m−2) following removal from incubation and similar changes in magnetic field intensity. Calculations indicated that the energy within the aqueous volume containing the cells was equivalent for that associated with the flux densities of the magnetic fields and the photon emissions. For every approximately 1 nT increase in magnetic field intensity value there was a decrease of ∼2 photons (equivalent of 10−18 J). These results complement correlation studies and suggest there may be a conservation of energy between expression as magnetic fields that are subtracted or added to the adjacent geomagnetic field and reciprocal changes in photon emissions when aggregates of cells within a specific volume of medium (water) adapt to new environments. PMID:26005634

  11. Quantitative structure-activity relationships and mixture toxicity of organic chemicals in Photobacterium phosphoreum: the Microtox test

    SciTech Connect

    Hermens, J.; Busser, F.; Leeuwangh, P.; Musch, A.

    1985-02-01

    Quantitative structure-activity relationships were calculated for the inhibition of bioluminescence of Photobacterium phosphoreum by 22 nonreactive organic chemicals. The inhibition was measured using the Microtox test and correlated with the partition coefficient between n-octanol and water (Poct), molar refractivity (MR), and molar volume (MW/d). At log Poct less than 1 and greater than 3, deviations from linearity were observed. Introduction of MR and MW/d improved the quality of the relationships. The influences of MR or MW/d may be related with an interaction of the tested chemicals to the enzyme system which produces the light emission. The sensitivity of the Microtox test to the 22 tested compounds is comparable to a 14-day acute mortality test with guppies for chemicals with log Poct less than 4. The inhibition of bioluminescence by a mixture of the tested compounds was slightly less than was expected in case of concentration addition. The Microtox test can give a good estimate of the total aspecific minimum toxicity of polluted waters. When rather lipophilic compounds or pollutants with more specific modes of action are present, this test will underestimate the toxicity to other aquatic life.

  12. A Quantitative Test for the Spatial Relationship Between Aftershock Distributions and Mainshock Rupture Properties

    NASA Astrophysics Data System (ADS)

    Woessner, J.; Ripperger, J.; Mai, M. P.; Wiemer, S.

    2004-12-01

    Correlating the properties of the mainshock rupture with the location of corresponding aftershocks may provide insight into the relationship between mainshock-induced static stress changes and aftershock occurrence. In this study, we develop a rigorous statistical test to quantify the spatial pattern of aftershock locations with the corresponding distributions of coseismic slip and stress-drop. Well-located aftershock hypocenters are projected onto the mainshock fault plane and coseismic slip and stress drop values are interpolated to their respective location. The null hypothesis H0 for the applied test statistic is: Aftershock hypocenters are randomly distributed on the mainshock fault plane and are not correlated with mainshock properties. Because we want to maintain spatial earthquake clustering as one of the important observed features of seismicity, we synthesize slip distributions using a random spatial field model from which we then compute the respective stress-drop distributions. For each simulation of earthquake slip, we compute the test statistic for the slip and stress-drop distribution, testing whether or not an apparent correlation between mainshock properties and aftershock locations exists. Uncertainties in the aftershock locations are accounted for by simulating a thousand catalogues for which we randomize the location of the aftershocks within their given location error bounds. We then determine the number of aftershocks in low-slip or negative stress-drop regions for simulated slip distributions, and compare those to the measurements obtained for finite-source slip inversions. We apply the test to crustal earthquakes in California and Japan. If possible, we use different source models and earthquake catalogues with varying accuracy to investigate the dependence of the test results on, for example, the location uncertainties of aftershocks. Contrary to the visual impression, we find that for some strike-slip earthquakes or segments of the

  13. The relationship between urban airborne pollution and short-term mortality: quantitative and qualitative aspects.

    PubMed

    Izzotti, A; Parodi, S; Quaglia, A; Farè, C; Vercelli, M

    2000-01-01

    The influence of airborne pollution on mortality rates has been examined since the well known severe pollution episodes of Pennsylvania (1948) and London (1952). Three main epidemiological approaches are available: transversal studies, time series studies, prospective studies. The most frequently used method is the time series analysis, which retrospectively determines daily mortality rates as compared to daily pollution levels in a defined period. The vast majority of studies applying this approach confirm the existence of a positive correlation between mortality and airborne pollution. The relative risk of death during the most severely polluted days as compared to the least polluted days ranges between 1.02 and 1.13. Airborne pollution affects mortality as related to cardiovascular and chronic obstructive pulmonary diseases mainly in subjects previously affected by these pathologies. The dose-response mortality-pollution curve shows linear increments of mortality at low pollution levels, weak increments at high pollution levels. This phenomenon is attributed to the existence of subjects highly susceptible to pollution induced adverse health effects. These subjects, dying at low pollution levels, are not available to increase mortality rates at high pollution levels. Mortality is mainly related to the concentration of single pollutants, such as suspended particle matter, sulfur oxides, nitric oxides and ozone. Elderly are highly susceptible to pollution-induced mortality increases. Therefore, the study of mortality-pollution correlation is of particular interest in cities characterized by a relative prevalence of the elderly in the population. The latency period between pollution increases and related mortality increases falls in the 1-3 days interval range. The pollution-mortality relationship is influenced by many factors, such as the occurrence of exceedingly high or low environmental temperatures, influenza epidemics, etc. Many hypotheses has been raised to

  14. Quantitative analysis of dose-effect relationships: the combined effects of multiple drugs or enzyme inhibitors.

    PubMed

    Chou, T C; Talalay, P

    1984-01-01

    A generalized method for analyzing the effects of multiple drugs and for determining summation, synergism and antagonism has been proposed. The derived, generalized equations are based on kinetic principles. The method is relatively simple and is not limited by whether the dose-effect relationships are hyperbolic or sigmoidal, whether the effects of the drugs are mutually exclusive or nonexclusive, whether the ligand interactions are competitive, noncompetitive or uncompetitive, whether the drugs are agonists or antagonists, or the number of drugs involved. The equations for the two most widely used methods for analyzing synergism, antagonism and summation of effects of multiple drugs, the isobologram and fractional product concepts, have been derived and been shown to have limitations in their applications. These two methods cannot be used indiscriminately. The equations underlying these two methods can be derived from a more generalized equation previously developed by us (59). It can be shown that the isobologram is valid only for drugs whose effects are mutually exclusive, whereas the fractional product method is valid only for mutually nonexclusive drugs which have hyperbolic dose-effect curves. Furthermore, in the isobol method, it is laborious to find proper combinations of drugs that would produce an iso-effective curve, and the fractional product method tends to give indication of synergism, since it underestimates the summation of the effect of mutually nonexclusive drugs that have sigmoidal dose-effect curves. The method described herein is devoid of these deficiencies and limitations. The simplified experimental design proposed for multiple drug-effect analysis has the following advantages: It provides a simple diagnostic plot (i.e., the median-effect plot) for evaluating the applicability of the data, and provides parameters that can be directly used to obtain a general equation for the dose-effect relation; the analysis which involves logarithmic

  15. Predicting Skin Permeability from Complex Chemical Mixtures: Dependency of Quantitative Structure Permeation Relationships on Biology of Skin Model Used

    PubMed Central

    Riviere, Jim E.; Brooks, James D.

    2011-01-01

    Dermal absorption of topically applied chemicals usually occurs from complex chemical mixtures; yet, most attempts to quantitate dermal permeability use data collected from single chemical exposure in aqueous solutions. The focus of this research was to develop quantitative structure permeation relationships (QSPR) for predicting chemical absorption from mixtures through skin using two levels of in vitro porcine skin biological systems. A total of 16 diverse chemicals were applied in 384 treatment mixture combinations in flow-through diffusion cells and 20 chemicals in 119 treatment combinations in isolated perfused porcine skin. Penetrating chemical flux into perfusate from diffusion cells was analyzed to estimate a normalized dermal absorptive flux, operationally an apparent permeability coefficient, and total perfusate area under the curve from perfused skin studies. These data were then fit to a modified dermal QSPR model of Abraham and Martin including a sixth term to account for mixture interactions based on physical chemical properties of the mixture components. Goodness of fit was assessed using correlation coefficients (r2), internal and external validation metrics (qLOO2, qL25%2, qEXT2), and applicable chemical domain determinations. The best QSPR equations selected for each experimental biological system had r2 values of 0.69–0.73, improving fits over the base equation without the mixture effects. Different mixture factors were needed for each model system. Significantly, the model of Abraham and Martin could also be reduced to four terms in each system; however, different terms could be deleted for each of the two biological systems. These findings suggest that a QSPR model for estimating percutaneous absorption as a function of chemical mixture composition is possible and that the nature of the QSPR model selected is dependent upon the biological level of the in vitro test system used, both findings having significant implications when dermal

  16. Quantitative Relationship Between Coronary Vasodilator Reserve Assessed by Rubidium-82 PET Imaging and Coronary Artery Stenosis Severity

    PubMed Central

    Anagnostopoulos, Constantinos; Almonacid, Alexandra; El Fakhri, Georges; Currilova, Zelmira; Sitek, Arkadiusz; Roughton, Michael; Dorbala, Sharmila; Popma, Jeffrey J.; Di Carli, Marcelo F.

    2011-01-01

    The relationship between myocardial blood flow (MBF) and stenosis severity has been determined previously using cyclotron-produced radiotracers such as 15O-H2O and 13N-ammonia. An attractive alternative to overcome the limitations related to the use of cyclotron might be to use the generator-produced Rubidium-82 as a flow tracer. The current study was undertaken to investigate the relationship between MBF and coronary vasodilator reserve (CVR) as measured by Rubidium-82 positron emission tomography (PET) and the percent diameter stenosis as defined by quantitative coronary arteriography. Methods We prospectively evaluated 22 individuals: 15 patients (60±11 years of age) with angiographically documented coronary artery disease (CAD) and seven age-matched (56±9 years) asymptomatic individuals without risk factors for CAD. Dynamic Rubidium-82 PET was performed at rest and after dipyridamole vasodilation. MBF, CVR and an index of “minimal coronary resistance” (MCR) were assessed in each of the three main coronary territories. Results Rest and stress MBF in regions subtended by vessels with <50% diameter stenosis was similar to that of the individuals with no risk factors for CAD. As a result, CVR was also similar in the two groups (1.9, interquartile [IQ] range from 1.7 to 2.7 vs. 2.2, IQ range from 2 to 3.4 respectively, p=0.09)). CVR successfully differentiated coronary lesions with stenosis severity 70% to 89% from those with 50% to 69% stenosis (1, IQ range from 1 to 1.3 vs. 1.7, IQ range from 1.4 to 2), respectively, p=0.001. In addition, hyperaemic MBF (r2=.74, p<0.001), CVR (r2=.69, p<0.001), and MCR (r2=.78, p<0.001) measurements were inversely and non-linearly correlated to the percent diameter stenosis on angiography. Conclusion MBF and CVR are inversely and non-linearly correlated to stenosis severity. Quantitative Rubidium-82 PET can be a clinically useful tool for an accurate functional assessment of CAD. PMID:18425513

  17. Relationships between regional economic sectors and water use in a water-scarce area in China: A quantitative analysis

    NASA Astrophysics Data System (ADS)

    Wang, Weiping; Gao, Lei; Liu, Pin; Hailu, Atakelty

    2014-07-01

    Northern China has been facing severe water scarcity as a result of vigorous economic growth, population expansion and changing lifestyles. A typical case is Shandong province whose water resources per capita is approximately only a sixth of the national average and a twentieth of the global average. It is useful to assess the implications of the province’s growth and trade patterns for water use and water conservation strategies. This study quantitatively analyses relationships between regional economic sectors and water use in Shandong using an input-output model for virtual water resources. The changes in key indicators for 1997-2007 are tracked and the effects of water-saving policies on these changes are examined. The results highlight the benefits of applying a virtual water trade analysis on a water-scarce region where water resources exhibit highly heterogeneous temporal and geographical distributions. The net export of virtual water in Shandong was initially large, but this declined over the years and the province has recently become a net importer. Between 1997 and 2002, water use in most sectors increased due to rapid urbanisation and industrialisation. Since then, water use in all Shandong economic sectors exhibit a downward trend despite continued increases in goods and services net exports, a trend which can be attributed to the vigorous implementation of water-saving policies and measures, especially water use quotas. Economic sectors consume water directly and indirectly and understanding the pattern of virtual water trade implied by sectoral relationships is important for managing water scarcity problems. This study fills the knowledge gap in the existing literature created by the lack of case studies that dynamically assess virtual water trade and analyse the effects of water-saving policies and measures. The study draws policy recommendations that are relevant for future water planning in Shandong and other regions in northern China.

  18. Verification of quantitative relationship among Birkeland current sheet motion, intensity, and convective velocity, and also of criterion for expansion onset

    SciTech Connect

    Atkinson, G.

    1986-08-01

    In this paper, 14 substorms are used to verify the conclusions of an earlier paper on current sheet motions. These conclusions can be summarized as follows: (1) The quantitative relationship V-italic/sub N-italic/ = V-italic/sub C-italic//sub N-italic/ -k-italic/sub V-italic/I-italic/sub parallel/ is valid when applied to the upward current sheet in the premidnight quadrant except during the expansion and early recovery phases of substorms (V-italic/sub i//sub N-italic/ and V-italic/sub C-italic//sub N-italic/ are the components, normal to the sheet, of the sheet velocity and the convection velocity, k-italic/sub v-italic/ is a constant, and I-italic/sub parallel/ is the current sheet intensity). (2) At the time of local northward expansion of the auroras there appears to be a decrease by 1 order of magnitude of the amount of plasma on the flux tubes. (3) The time of initiation of local northward expansion occurs when V-italic/sub C-italic//sub N-italic/ = k-italic/sub V-italic/I-italic/sub parallel/. A few additional points emerge from this study: The above relationships are not valid at stations east of the location of initial onset of expansion, and the amount of plasma on flux tubes tends to return to its preexpansion value after a substorm. Further conclusions are (1) that the physical mechanism responsible for the northward expansion in a westward traveling surge is the same as in the initial near-midnight expansion, (2) that the triggering of expansion occurs just as the tail begins to recede away from the earth, and (3) that the apparent decrease in plasma content is consistent with the formation of a near-earth neutral line; however, it could also result from the breakdown of the sheet approximation for the currents.

  19. Modeling the reactivities of hydroxyl radical and ozone towards atmospheric organic chemicals using quantitative structure-reactivity relationship approaches.

    PubMed

    Gupta, Shikha; Basant, Nikita; Mohan, Dinesh; Singh, Kunwar P

    2016-07-01

    The persistence and the removal of organic chemicals from the atmosphere are largely determined by their reactions with the OH radical and O3. Experimental determinations of the kinetic rate constants of OH and O3 with a large number of chemicals are tedious and resource intensive and development of computational approaches has widely been advocated. Recently, ensemble machine learning (EML) methods have emerged as unbiased tools to establish relationship between independent and dependent variables having a nonlinear dependence. In this study, EML-based, temperature-dependent quantitative structure-reactivity relationship (QSRR) models have been developed for predicting the kinetic rate constants for OH (kOH) and O3 (kO3) reactions with diverse chemicals. Structural diversity of chemicals was evaluated using a Tanimoto similarity index. The generalization and prediction abilities of the constructed models were established through rigorous internal and external validation performed employing statistical checks. In test data, the EML QSRR models yielded correlation (R (2)) of ≥0.91 between the measured and the predicted reactivities. The applicability domains of the constructed models were determined using methods based on descriptors range, Euclidean distance, leverage, and standardization approaches. The prediction accuracies for the higher reactivity compounds were relatively better than those of the low reactivity compounds. Proposed EML QSRR models performed well and outperformed the previous reports. The proposed QSRR models can make predictions of rate constants at different temperatures. The proposed models can be useful tools in predicting the reactivities of chemicals towards OH radical and O3 in the atmosphere. PMID:27040550

  20. Structural alerts for predicting clastogenic activity of pro-oxidant flavonoid compounds: quantitative structure-activity relationship study.

    PubMed

    Yordi, Estela Guardado; Pérez, Enrique Molina; Matos, Maria Joao; Villares, Eugenio Uriarte

    2012-02-01

    Flavonoids have been reported to exert multiple biological effects that include acting as pro-oxidants at very high doses. The authors determined a structural alert to identify the clastogenic activity of a series of flavonoids with pro-oxidant activity. The methodology was based on a quantitative structure-activity relationship (QSAR) study. Specifically, the authors developed a virtual screening method for a clastogenic model using the topological substructural molecular design (TOPS-MODE) approach. It represents a useful platform for the automatic generation of structural alerts, based on the calculation of spectral moments of molecular bond matrices appropriately weighted, taking into account the hydrophobic, electronic, and steric molecular features. Therefore, it was possible to establish the structural criteria for maximal clastogenicity of pro-oxidant flavonoids: the presence of a 3-hydroxyl group and a 4-carbonyl group in ring C, the maximal number of hydroxyl groups in ring B, the presence of methoxyl and phenyl groups, the absence of a 2,3-double bond in ring C, and the presence of 5,7 hydroxyl groups in ring A. The presented clastogenic model may be useful for screening new pro-oxidant compounds. This alert could help in the design of new and efficient flavonoids, which could be used as bioactive compounds in nutraceuticals and functional food. PMID:21940715

  1. Development of quantitative structure activity relationship (QSAR) model for disinfection byproduct (DBP) research: A review of methods and resources.

    PubMed

    Chen, Baiyang; Zhang, Tian; Bond, Tom; Gan, Yiqun

    2015-12-15

    Quantitative structure-activity relationship (QSAR) models are tools for linking chemical activities with molecular structures and compositions. Due to the concern about the proliferating number of disinfection byproducts (DBPs) in water and the associated financial and technical burden, researchers have recently begun to develop QSAR models to investigate the toxicity, formation, property, and removal of DBPs. However, there are no standard procedures or best practices regarding how to develop QSAR models, which potentially limit their wide acceptance. In order to facilitate more frequent use of QSAR models in future DBP research, this article reviews the processes required for QSAR model development, summarizes recent trends in QSAR-DBP studies, and shares some important resources for QSAR development (e.g., free databases and QSAR programs). The paper follows the four steps of QSAR model development, i.e., data collection, descriptor filtration, algorithm selection, and model validation; and finishes by highlighting several research needs. Because QSAR models may have an important role in progressing our understanding of DBP issues, it is hoped that this paper will encourage their future use for this application. PMID:26142156

  2. The signature molecular descriptor. 3. Inverse-quantitative structure-activity relationship of ICAM-1 inhibitory peptides.

    PubMed

    Churchwell, Carla J; Rintoul, Mark D; Martin, Shawn; Visco, Donald P; Kotu, Archana; Larson, Richard S; Sillerud, Laurel O; Brown, David C; Faulon, Jean-Loup

    2004-03-01

    We present a methodology for solving the inverse-quantitative structure-activity relationship (QSAR) problem using the molecular descriptor called signature. This methodology is detailed in four parts. First, we create a QSAR equation that correlates the occurrence of a signature to the activity values using a stepwise multilinear regression technique. Second, we construct constraint equations, specifically the graphicality and consistency equations, which facilitate the reconstruction of the solution compounds directly from the signatures. Third, we solve the set of constraint equations, which are both linear and Diophantine in nature. Last, we reconstruct and enumerate the solution molecules and calculate their activity values from the QSAR equation. We apply this inverse-QSAR method to a small set of LFA-1/ICAM-1 peptide inhibitors to assist in the search and design of more-potent inhibitory compounds. Many novel inhibitors were predicted, a number of which are predicted to be more potent than the strongest inhibitor in the training set. Two of the more potent inhibitors were synthesized and tested in-vivo, confirming them to be the strongest inhibiting peptides to date. Some of these compounds can be recycled to train a new QSAR and develop a more focused library of lead compounds. PMID:15177078

  3. Synthesis, biological evaluation, mechanism of action and quantitative structure-activity relationship studies of chalcones as antibacterial agents.

    PubMed

    Sivakumar, Ponnurengam Malliappan; Priya, Sobana; Doble, Mukesh

    2009-04-01

    Forty-eight chalcone analogs were synthesized and their in vitro antibacterial activity against Staphylococcus aureus NCIM 5021, Bacillus subtilis NCIM 2718, Phaseolus vulgaris NCIM 2813, Escherichia coli NCIM 2931, Salmonella typhi 2501 and Enterobacter aerogenes NCIM 5139 were evaluated by microdilution broth assay. Quantitative structure-activity relationships were developed for all the cases (r(2) = 0.68-0.79; r(2)(adj) = 0.58-0.78; q(2) = 0.51-0.68; F = 13.02-61.51). Size, polarizability, electron-donating/withdrawing and hydrophilic nature of the molecule determine the activity against these Gram-positive and Gram-negative bacteria. Staphylococcus aureus was the most and S. typhi was the least hydrophobic of these organisms. These chalcones act better against more hydrophobic organisms. The more active chalcones have log P between 1.5 and 3. Compound 24, one of the most active compounds, was found to act by damaging the cell wall of S. aureus. Slimicidal activity of five of the most active compounds (24, 31, 32, 34 and 37) was found to be in the range of 48-60% against S. aureus and 40-54% against E. coli. A correlation was observed among the hydrophobicity of the compounds, hydrophobicity of the bacterial cell surface and the antibacterial activity of the compound. PMID:19291103

  4. Quantitative structure-activity relationships of the antimalarial agent artemisinin and some of its derivatives - a DFT approach.

    PubMed

    Rajkhowa, Sanchaita; Hussain, Iftikar; Hazarika, Kalyan K; Sarmah, Pubalee; Deka, Ramesh Chandra

    2013-09-01

    Artemisinin form the most important class of antimalarial agents currently available, and is a unique sesquiterpene peroxide occurring as a constituent of Artemisia annua. Artemisinin is effectively used in the treatment of drug-resistant Plasmodium falciparum and because of its rapid clearance of cerebral malaria, many clinically useful semisynthetic drugs for severe and complicated malaria have been developed. However, one of the major disadvantages of using artemisinins is their poor solubility either in oil or water and therefore, in order to overcome this difficulty many derivatives of artemisinin were prepared. A comparative study on the chemical reactivity of artemisinin and some of its derivatives is performed using density functional theory (DFT) calculations. DFT based global and local reactivity descriptors, such as hardness, chemical potential, electrophilicity index, Fukui function, and local philicity calculated at the optimized geometries are used to investigate the usefulness of these descriptors for understanding the reactive nature and reactive sites of the molecules. Multiple regression analysis is applied to build up a quantitative structure-activity relationship (QSAR) model based on the DFT based descriptors against the chloroquine-resistant, mefloquine-sensitive Plasmodium falciparum W-2 clone. PMID:23597248

  5. Quantitative structure-activity relationship analysis of substituted arylazo pyridone dyes in photocatalytic system: Experimental and theoretical study.

    PubMed

    Dostanić, J; Lončarević, D; Zlatar, M; Vlahović, F; Jovanović, D M

    2016-10-01

    A series of arylazo pyridone dyes was synthesized by changing the type of the substituent group in the diazo moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The structural and electronic properties of the investigated dyes was calculated at the M062X/6-31+G(d,p) level of theory. The observed good linear correlations between atomic charges and Hammett σp constants provided a basis to discuss the transmission of electronic substituent effects through a dye framework. The reactivity of synthesized dyes was tested through their decolorization efficiency in TiO2 photocatalytic system (Degussa P-25). Quantitative structure-activity relationship analysis revealed a strong correlation between reactivity of investigated dyes and Hammett substituent constants. The reaction was facilitated by electron-withdrawing groups, and retarded by electron-donating ones. Quantum mechanical calculations was used in order to describe the mechanism of the photocatalytic oxidation reactions of investigated dyes and interpret their reactivities within the framework of the Density Functional Theory (DFT). According to DFT based reactivity descriptors, i.e. Fukui functions and local softness, the active site moves from azo nitrogen atom linked to benzene ring to pyridone carbon atom linked to azo bond, going from dyes with electron-donating groups to dyes with electron-withdrawing groups. PMID:27209516

  6. Natural products as insecticides: the biology, biochemistry and quantitative structure-activity relationships of spinosyns and spinosoids.

    PubMed

    Sparks, T C; Crouse, G D; Durst, G

    2001-10-01

    The spinosyns, a novel family of insecticidal macrocyclic lactones, are active on a wide variety of insect pests, especially lepidopterans and dipterans. The biological activity of a mixture (spinosad; Tracer, Spin-Tor, Success) of the two most abundant spinosyns (spinosyns A and D) against pest insects is on a par with that of many pyrethroid insecticides. The spinosyns also exhibit a very favorable environmental and toxicological profile, and possess a mode of action that appears unique, with studies to date suggesting that both nicotinic and gamma-aminobutryic acid receptor functions are altered in a novel manner. Compared to pyrethroids such as cypermethrin, spinosyn A is slow to penetrate into insect larvae such as tobacco budworm larvae (Heliothis virescens); however, once inside the insect, spinosyn A is not readily metabolized. To date, more than 20 spinosyns and more than 800 spinosoids (semi-synthetic analogs) have been isolated or synthesized, respectively. Artificial neural network-based quantitative structure activity relationship (QSAR) studies for the spinosyns suggested that modification of the 2',3',4'-tri-O-methylrhamnosyl moiety could improve activity and several spinosoids incorporating these modifications exhibited markedly improved lepidopteran activity compared to spinosad. Multiple linear regression-based QSAR studies also suggest that whole molecule properties such as CLogP and MOPAC dipole moment can explain much of the biological activity observed for the spinosyns and closely related spinosoids. PMID:11695182

  7. Quantitative Genome-Wide Genetic Interaction Screens Reveal Global Epistatic Relationships of Protein Complexes in Escherichia coli

    PubMed Central

    Kumar, Ashwani; Stewart, Geordie; Samanfar, Bahram; Aoki, Hiroyuki; Wagih, Omar; Vlasblom, James; Phanse, Sadhna; Lad, Krunal; Yeou Hsiung Yu, Angela; Graham, Christopher; Jin, Ke; Brown, Eric; Golshani, Ashkan; Kim, Philip; Moreno-Hagelsieb, Gabriel; Greenblatt, Jack; Houry, Walid A.; Parkinson, John; Emili, Andrew

    2014-01-01

    Large-scale proteomic analyses in Escherichia coli have documented the composition and physical relationships of multiprotein complexes, but not their functional organization into biological pathways and processes. Conversely, genetic interaction (GI) screens can provide insights into the biological role(s) of individual gene and higher order associations. Combining the information from both approaches should elucidate how complexes and pathways intersect functionally at a systems level. However, such integrative analysis has been hindered due to the lack of relevant GI data. Here we present a systematic, unbiased, and quantitative synthetic genetic array screen in E. coli describing the genetic dependencies and functional cross-talk among over 600,000 digenic mutant combinations. Combining this epistasis information with putative functional modules derived from previous proteomic data and genomic context-based methods revealed unexpected associations, including new components required for the biogenesis of iron-sulphur and ribosome integrity, and the interplay between molecular chaperones and proteases. We find that functionally-linked genes co-conserved among γ-proteobacteria are far more likely to have correlated GI profiles than genes with divergent patterns of evolution. Overall, examining bacterial GIs in the context of protein complexes provides avenues for a deeper mechanistic understanding of core microbial systems. PMID:24586182

  8. Quantitative relationships between structure and cytotoxic activity of flavonoid derivatives. An application of Hirshfeld surface derived descriptors.

    PubMed

    Kupcewicz, Bogumiła; Małecka, Magdalena; Zapadka, Mariusz; Krajewska, Urszula; Rozalski, Marek; Budzisz, Elzbieta

    2016-07-15

    Quantitative relationships between the structure and cytotoxic activity of series flavonoid derivatives were examined. The first regression-based model, developed for 18 flavanone-2-pyrazoline hybrids, involved two interpretable descriptors: a Mor04v and partial atomic charge. The second model, developed for structurally diverse set of compounds, was based on descriptors derived from Hirshfeld surface analysis. This model suggests that cytotoxic activity of compounds can be successfully predicted based on a fraction of H⋯H contacts and a fraction of interactions involving a halogen atom. For non-halogen derivatives, the data reveal that cytotoxic activity is inversely proportional to the percentage of O⋯H and N⋯H close contacts to Hirshfeld surface, while directly proportional to the percentage of H⋯H interactions. Chlorine (1k) and bromine (1l) derivatives of compounds, containing flavanone fused with N-methyl-2-pyrazoline, exhibited high cytotoxic potential against HL-60 cancer cell line (IC50<10μM). The cytotoxicity of 1k and 1l towards normal cells (HUVEC) was 10 and 25-fold lower, respectively. PMID:27234147

  9. Synthetic cannabinoids: In silico prediction of the cannabinoid receptor 1 affinity by a quantitative structure-activity relationship model.

    PubMed

    Paulke, Alexander; Proschak, Ewgenij; Sommer, Kai; Achenbach, Janosch; Wunder, Cora; Toennes, Stefan W

    2016-03-14

    The number of new synthetic psychoactive compounds increase steadily. Among the group of these psychoactive compounds, the synthetic cannabinoids (SCBs) are most popular and serve as a substitute of herbal cannabis. More than 600 of these substances already exist. For some SCBs the in vitro cannabinoid receptor 1 (CB1) affinity is known, but for the majority it is unknown. A quantitative structure-activity relationship (QSAR) model was developed, which allows the determination of the SCBs affinity to CB1 (expressed as binding constant (Ki)) without reference substances. The chemically advance template search descriptor was used for vector representation of the compound structures. The similarity between two molecules was calculated using the Feature-Pair Distribution Similarity. The Ki values were calculated using the Inverse Distance Weighting method. The prediction model was validated using a cross validation procedure. The predicted Ki values of some new SCBs were in a range between 20 (considerably higher affinity to CB1 than THC) to 468 (considerably lower affinity to CB1 than THC). The present QSAR model can serve as a simple, fast and cheap tool to get a first hint of the biological activity of new synthetic cannabinoids or of other new psychoactive compounds. PMID:26795018

  10. A quantitative structure-activity relationship to predict efficacy of granular activated carbon adsorption to control emerging contaminants.

    PubMed

    Kennicutt, A R; Morkowchuk, L; Krein, M; Breneman, C M; Kilduff, J E

    2016-08-01

    A quantitative structure-activity relationship was developed to predict the efficacy of carbon adsorption as a control technology for endocrine-disrupting compounds, pharmaceuticals, and components of personal care products, as a tool for water quality professionals to protect public health. Here, we expand previous work to investigate a broad spectrum of molecular descriptors including subdivided surface areas, adjacency and distance matrix descriptors, electrostatic partial charges, potential energy descriptors, conformation-dependent charge descriptors, and Transferable Atom Equivalent (TAE) descriptors that characterize the regional electronic properties of molecules. We compare the efficacy of linear (Partial Least Squares) and non-linear (Support Vector Machine) machine learning methods to describe a broad chemical space and produce a user-friendly model. We employ cross-validation, y-scrambling, and external validation for quality control. The recommended Support Vector Machine model trained on 95 compounds having 23 descriptors offered a good balance between good performance statistics, low error, and low probability of over-fitting while describing a wide range of chemical features. The cross-validated model using a log-uptake (qe) response calculated at an aqueous equilibrium concentration (Ce) of 1 μM described the training dataset with an r(2) of 0.932, had a cross-validated r(2) of 0.833, and an average residual of 0.14 log units. PMID:27586364

  11. Estimating the Potential Toxicity of Chemicals Associated with Hydraulic Fracturing Operations Using Quantitative Structure-Activity Relationship Modeling.

    PubMed

    Yost, Erin E; Stanek, John; DeWoskin, Robert S; Burgoon, Lyle D

    2016-07-19

    The United States Environmental Protection Agency (EPA) identified 1173 chemicals associated with hydraulic fracturing fluids, flowback, or produced water, of which 1026 (87%) lack chronic oral toxicity values for human health assessments. To facilitate the ranking and prioritization of chemicals that lack toxicity values, it may be useful to employ toxicity estimates from quantitative structure-activity relationship (QSAR) models. Here we describe an approach for applying the results of a QSAR model from the TOPKAT program suite, which provides estimates of the rat chronic oral lowest-observed-adverse-effect level (LOAEL). Of the 1173 chemicals, TOPKAT was able to generate LOAEL estimates for 515 (44%). To address the uncertainty associated with these estimates, we assigned qualitative confidence scores (high, medium, or low) to each TOPKAT LOAEL estimate, and found 481 to be high-confidence. For 48 chemicals that had both a high-confidence TOPKAT LOAEL estimate and a chronic oral reference dose from EPA's Integrated Risk Information System (IRIS) database, Spearman rank correlation identified 68% agreement between the two values (permutation p-value =1 × 10(-11)). These results provide support for the use of TOPKAT LOAEL estimates in identifying and prioritizing potentially hazardous chemicals. High-confidence TOPKAT LOAEL estimates were available for 389 of 1026 hydraulic fracturing-related chemicals that lack chronic oral RfVs and OSFs from EPA-identified sources, including a subset of chemicals that are frequently used in hydraulic fracturing fluids. PMID:27172125

  12. Quantitative Relationship of Soil Texture with the Observed Population Density Reduction of Heterodera glycines after Annual Corn Rotation in Nebraska

    PubMed Central

    Pérez-Hernández, Oscar; Giesler, Loren J.

    2014-01-01

    Soil texture has been commonly associated with the population density of Heterodera glycines (soybean cyst nematode: SCN), but such an association has been mainly described in terms of textural classes. In this study, multivariate analysis and a generalized linear modeling approach were used to elucidate the quantitative relationship of soil texture with the observed SCN population density reduction after annual corn rotation in Nebraska. Forty-five commercial production fields were sampled in 2009, 2010, and 2011 and SCN population density (eggs/100 cm3 of soil) for each field was determined before (Pi) and after (Pf) annual corn rotation from ten 3 × 3-m sampling grids. Principal components analysis revealed that, compared with silt and clay, sand had a stronger association with SCN Pi and Pf. Cluster analysis using the average linkage method and confirmed through 1,000 bootstrap simulations identified two groups: one corresponding to predominant silt-and-clay fields and other to sand-predominant fields. This grouping suggested that SCN relative percent population decline was higher in the sandy than in the silt-and-clay predominant group. However, when groups were compared for their SCN population density reduction using Pf as the response, Pi as a covariate, and incorporating the year and field variability, a negative binomial generalized linear model indicated that the SCN population density reduction was not statistically different between the sand-predominant field group and the silt-and-clay predominant group. PMID:24987160

  13. Quantitative Structure-Activity Relationships Study on the Rate Constants of Polychlorinated Dibenzo-p-Dioxins with OH Radical

    PubMed Central

    Qi, Chuansong; Zhang, Chenxi; Sun, Xiaomin

    2015-01-01

    The OH-initiated reaction rate constants (kOH) are of great importance to measure atmospheric behaviors of polychlorinated dibenzo-p-dioxins (PCDDs) in the environment. The rate constants of 75 PCDDs with the OH radical at 298.15 K have been calculated using high level molecular orbital theory, and the rate constants (kα, kβ, kγ and kOH) were further analyzed by the quantitative structure-activity relationships (QSAR) study. According to the QSAR models, the relations between rate constants and the numbers and positions of Cl atoms, the energy of the highest occupied molecular orbital (EHOMO), the energy of the lowest unoccupied molecular orbital (ELUMO), the difference ΔEHOMO-LUMO between EHOMO and ELUMO, and the dipole of oxidizing agents (D) were discussed. It was found that EHOMO is the main factor in the kOH. The number of Cl atoms is more effective than the number of relative position of these Cl atoms in the kOH. The kOH decreases with the increase of the substitute number of Cl atoms. PMID:26274950

  14. Ecotoxicity quantitative structure-activity relationships for alcohol ethoxylate mixtures based on substance-specific toxicity predictions.

    PubMed

    Boeije, G M; Cano, M L; Marshall, S J; Belanger, S E; Van Compernolle, R; Dorn, P B; Gümbel, H; Toy, R; Wind, T

    2006-05-01

    Traditionally, ecotoxicity quantitative structure-activity relationships (QSARs) for alcohol ethoxylate (AE) surfactants have been developed by assigning the measured ecotoxicity for commercial products to the average structures (alkyl chain length and ethoxylate chain length) of these materials. Acute Daphnia magna toxicity tests for binary mixtures indicate that mixtures are more toxic than the individual AE substances corresponding with their average structures (due to the nonlinear relation of toxicity with structure). Consequently, the ecotoxicity value (expressed as effects concentration) attributed to the average structures that are used to develop the existing QSARs is expected to be too low. A new QSAR technique for complex substances, which interprets the mixture toxicity with regard to the "ethoxymers" distribution (i.e., the individual AE components) rather than the average structure, was developed. This new technique was then applied to develop new AE ecotoxicity QSARs for invertebrates, fish, and mesocosms. Despite the higher complexity, the fit and accuracy of the new QSARs are at least as good as those for the existing QSARs based on the same data set. As expected from typical ethoxymer distributions of commercial AEs, the new QSAR generally predicts less toxicity than the QSARs based on average structure. PMID:16256196

  15. Dose-survival relationship for epithelial cells of human skin after multifraction irradiation: evaluation by a quantitative method in vivo

    SciTech Connect

    Arcangeli, G.; Mauro, F.; Nervi, C.; Withers, H.R.

    1980-07-01

    The dose-survival relationship for normal epithelial cells after single and fractionated radiation exposures has been established by Withers for the mouse, but it is not available for humans according to a strict criterion for survival of single cell reproductive integrity. In an attempt to obtain such a quantitative estimation, 2 patients requiring radical radiation therapy to the chest wall were treated according to particular Multiple Daily Fractionation (MDF) protocols: i) 250 + 150 + 150 rad/day, 4 hr interval, 5 days/week; and ii) 150 + 150 + 150 + 150 rad/day, 3.5 hr interval, 5 days/week. In both cases, different strips of skin received different total doses: 6300, 6850, and 7150 rad, and 6300, 6750, and 7200 rad, respectively. In case (i), moist desquamation appeared and thereafter repopulating colonies of epithelium could be recognized and counted. Using these counts a survival curve having a D/sub o/ value of 490 +- 150 rad was estimated according to the formula proposed by Withers. In case (ii), no moist desquamation was reached at the doses delivered. The difference observed may imply that the initial region of the survival curve deviates appreciably from exponential between doses of 150 and 250 rad. If such is the case, a /sub 1/D/sub o/ value of 490 rad may represent an underestimate. These results are discussed from the point of view of both the shape of the survival curve and the effectiveness of nonconventional fractionation courses.

  16. A Quantitative Structure Activity Relationship for acute oral toxicity of pesticides on rats: Validation, domain of application and prediction.

    PubMed

    Hamadache, Mabrouk; Benkortbi, Othmane; Hanini, Salah; Amrane, Abdeltif; Khaouane, Latifa; Si Moussa, Cherif

    2016-02-13

    Quantitative Structure Activity Relationship (QSAR) models are expected to play an important role in the risk assessment of chemicals on humans and the environment. In this study, we developed a validated QSAR model to predict acute oral toxicity of 329 pesticides to rats because a few QSAR models have been devoted to predict the Lethal Dose 50 (LD50) of pesticides on rats. This QSAR model is based on 17 molecular descriptors, and is robust, externally predictive and characterized by a good applicability domain. The best results were obtained with a 17/9/1 Artificial Neural Network model trained with the Quasi Newton back propagation (BFGS) algorithm. The prediction accuracy for the external validation set was estimated by the Q(2)ext and the root mean square error (RMS) which are equal to 0.948 and 0.201, respectively. 98.6% of external validation set is correctly predicted and the present model proved to be superior to models previously published. Accordingly, the model developed in this study provides excellent predictions and can be used to predict the acute oral toxicity of pesticides, particularly for those that have not been tested as well as new pesticides. PMID:26513561

  17. Molecular descriptor subset selection in theoretical peptide quantitative structure-retention relationship model development using nature-inspired optimization algorithms.

    PubMed

    Žuvela, Petar; Liu, J Jay; Macur, Katarzyna; Bączek, Tomasz

    2015-10-01

    In this work, performance of five nature-inspired optimization algorithms, genetic algorithm (GA), particle swarm optimization (PSO), artificial bee colony (ABC), firefly algorithm (FA), and flower pollination algorithm (FPA), was compared in molecular descriptor selection for development of quantitative structure-retention relationship (QSRR) models for 83 peptides that originate from eight model proteins. The matrix with 423 descriptors was used as input, and QSRR models based on selected descriptors were built using partial least squares (PLS), whereas root mean square error of prediction (RMSEP) was used as a fitness function for their selection. Three performance criteria, prediction accuracy, computational cost, and the number of selected descriptors, were used to evaluate the developed QSRR models. The results show that all five variable selection methods outperform interval PLS (iPLS), sparse PLS (sPLS), and the full PLS model, whereas GA is superior because of its lowest computational cost and higher accuracy (RMSEP of 5.534%) with a smaller number of variables (nine descriptors). The GA-QSRR model was validated initially through Y-randomization. In addition, it was successfully validated with an external testing set out of 102 peptides originating from Bacillus subtilis proteomes (RMSEP of 22.030%). Its applicability domain was defined, from which it was evident that the developed GA-QSRR exhibited strong robustness. All the sources of the model's error were identified, thus allowing for further application of the developed methodology in proteomics. PMID:26346190

  18. An advanced application of the quantitative structure-activity relationship concept in electrokinetic chromatography of metal complexes.

    PubMed

    Oszwałdowski, Sławomir; Timerbaev, Andrei R

    2008-02-01

    The relevance of the quantitative structure-activity relationship (QSAR) principle in MEKC and microemulsion EKC (MEEKC) of metal-ligand complexes was evaluated for a better understanding of analyte migration mechanism. A series of gallium chelates were applied as test solutes with available experimental migration data in order to reveal the molecular properties that govern the separation. The QSAR models operating with n-octanol-water partition coefficients or van der Waals volumes were found to be valid for estimation of the retention factors (log k') of neutral compounds when using only an aqueous MEEKC electrolyte. On the other hand, consistent approximations of log k' for both uncharged and charged complexes in either EKC mode (and also with hydro-organic BGEs) were achievable with two-parametric QSARs in which the dipole moment is additionally incorporated as a structural descriptor, reflecting the electrostatic solute-pseudostationary phase interaction. The theoretical analysis of significant molecular parameters in MEKC systems, in which the micellar BGE is modified with an organic solvent, confirmed that concomitant consideration of hydrophobic, electrostatic, and solvation factors is essential for explaining the migration behavior of neutral metal complexes. PMID:18219650

  19. High-pressure structural properties of tetramethylsilane

    NASA Astrophysics Data System (ADS)

    Zhen-Xing, Qin; Xiao-Jia, Chen

    2016-02-01

    High-pressure structural properties of tetramethylsilane are investigated by synchrotron powder x-ray diffraction at pressures up to 31.1 GPa and room temperature. A phase with the space group of Pnma is found to appear at 4.2 GPa. Upon compression, the compound transforms to two following phases: the phase with space groups of P21/c at 9.9 GPa and the phase with P2/m at 18.2 GPa successively via a transitional phase. The unique structural character of P21/c supports the phase stability of tetramethylsilane without possible decomposition upon heavy compression. The appearance of the P2/m phase suggests the possible realization of metallization for this material at higher pressure. Project supported by the Cultivation Fund of the Key Scientific and Technical Innovation Project from Ministry of Education of China (Grant No. 708070), the Fundamental Research Funds for the Central Universities, South China University of Technology (Grant No. 2014ZZ0069), the National Natural Science Foundation of China (Grant No. 51502189), and the Doctoral Project of Taiyuan University of Science and Technology, China (Grant No. 20132010).

  20. Structural properties of hexagonal boron nitride

    NASA Astrophysics Data System (ADS)

    Ooi, N.; Rajan, V.; Gottlieb, J.; Catherine, Y.; Adams, J. B.

    2006-04-01

    The electronic and structural properties of hexagonal boron nitride (BN) were studied using density functional theory calculations. Three different approximations for the exchange—correlation energy (the local density and two forms of the generalized gradient)—were used to calculate properties such as the bulk modulus, cohesive energy and lattice constants to determine their relative predictive abilities for this system. In general, calculations using the local density approximation produced properties slightly closer to experimental values than calculations with either generalized gradient approximations. Different stackings, or arrangements of one basal plane with respect to another, were examined to determine the equilibrium stacking(s) and it was found that the different stackings have similar cohesive energies and bulk moduli. Energy versus volume curves were calculated for each stacking using two different methods to determine their relative efficacy. Bulk moduli values obtained assuming no pressure dependence were closer to experimental values than those obtained from three common equations of state. Comparisons between the cohesive energies of hexagonal BN and cubic BN show that the cubic phase is more stable. The pressure/volume dependence of the band structure was studied for several different stackings and all showed similar behaviour, specifically a 3-4.5 eV band gap that was nearly independent of pressure in the -500 to +500 kb regime. These calculated results of the pressure/volume dependence of the band structure are the first reports for this system.

  1. Structural properties of spatially embedded networks

    NASA Astrophysics Data System (ADS)

    Kosmidis, K.; Havlin, S.; Bunde, A.

    2008-05-01

    We study the effects of spatial constraints on the structural properties of networks embedded in one- or two-dimensional space. When nodes are embedded in space, they have a well-defined Euclidean distance r between any pair. We assume that nodes at distance r have a link with probability p(r)~r-δ. We study the mean topological distance l and the clustering coefficient C of these networks and find that they both exhibit phase transitions for some critical value of the control parameter δ depending on the dimensionality d of the embedding space. We have identified three regimes. When δ2d the networks are "large" worlds l~N1/d with high clustering. Our results indicate that spatial constrains have a significant impact on the network properties, a fact that should be taken into account when modeling complex networks.

  2. Molecular-orbital analysis of the electronic structure and determination of quantitative structure-activity and structure-toxicity relationships for water-soluble ionol derivatives

    SciTech Connect

    Bushelev, S.N.

    1985-08-01

    In this paper the authors attempt to establish a quantitative relationship between experimental data on antitumor activity and the toxicity of ionol and its derivatives on the one hand, and on the other hand the electronic structure parameters of the compounds obtained as a result of the quantum chemical calculation.

  3. Parental Involvement and Student Motivation: A Quantitative Study of the Relationship between Student Goal Orientation and Student Perceptions of Parental Involvement among 5th Grade Students

    ERIC Educational Resources Information Center

    Mendoza, Christine Daryabigi

    2012-01-01

    The purpose of this study was to examine a possible relationship between student perceptions of parental involvement and student goal orientation for an ethnically diverse fifth grade elementary population from high-poverty schools. This study was quantitative in nature and employed the Patterns of Adaptive Learning Scales (PALS) to assess the…

  4. Quantitative structure-activity relationship models with receptor-dependent descriptors for predicting peroxisome proliferator-activated receptor activities of thiazolidinedione and oxazolidinedione derivatives.

    PubMed

    Lather, Viney; Kairys, Visvaldas; Fernandes, Miguel X

    2009-04-01

    A quantitative structure-activity relationship study has been carried out, in which the relationship between the peroxisome proliferator-activated receptor alpha and the peroxisome proliferator-activated receptor gamma agonistic activities of thiazolidinedione and oxazolidinedione derivatives and quantitative descriptors, V(site) calculated in a receptor-dependent manner is modeled. These descriptors quantify the volume occupied by the optimized ligands in regions that are either common or specific to the superimposed binding sites of the targets under consideration. The quantitative structure-activity relationship models were built by forward stepwise linear regression modeling for a training set of 27 compounds and validated for a test set of seven compounds, resulting in a squared correlation coefficient value of 0.90 for peroxisome proliferator-activated receptor alpha and of 0.89 for peroxisome proliferator-activated receptor gamma. The leave-one-out cross-validation and test set predictability squared correlation coefficient values for these models were 0.85 and 0.62 for peroxisome proliferator-activated receptor alpha and 0.89 and 0.50 for peroxisome proliferator-activated receptor gamma respectively. A dual peroxisome proliferator-activated receptor model has also been developed, and it indicates the structural features required for the design of ligands with dual peroxisome proliferator-activated receptor activity. These quantitative structure-activity relationship models show the importance of the descriptors here introduced in the prediction and interpretation of the compounds affinity and selectivity. PMID:19243388

  5. [Near surface CO2 concentration and its quantitative relationship with character of underlying surface in Shanghai City, China].

    PubMed

    Pan, Chen; Zhu, Xi-yang; Jia, Wen-xiao; Yang, Fang; Liu, Ming; Xiang, Wei-ning

    2015-07-01

    Land use change and fossil fuel combustion due to urbanization have a significant effect on global carbon cycle and climate change. It's important to have an explicit understanding of the spatial distribution of CO2 to recognize and control GHG emission, which is helpful to reduce human-induced contribution to global climate change. The study area of this project was set in the city of Shanghai with intensive human activity and rapid urbanization. The monitoring of near surface CO2 concentration along 3 transects was conducted across an urban-rural gradient by means of near infrared gas analyzer Li-840A in spring, 2014. Remote sensing data were also used to derive underlying surface information. Further quantitative analysis of the mechanism of CO2 concentration's response to the characteristics of underlying surface was presented in this paper. The results showed that the average near surface CO2 concentration was (443.4±22.0) µmol . mol-1. CO2 concentration in city center was in average 12.5% (52.5 µLmol . mol-1) higher than that in the suburban area. Also, CO2 concentration showed a significant spatial differentiation, with the highest CO2 concentration in the northwest, the second highest in the southwest, and the lowest in the southeast, which was in accordance with the urbanization level of the underlying surface. The results revealed that the vegetation coverage rate (CVeg) was an important indicator to describe near surface CO2 concentration with a negative correlation, and the impervious surface area coverage rate (CISA) had lower explanatory power with a positive correlation. The study also found that the determination coefficient (R2) between CO2 concentration (CCO2) and CISA or CVeg achieved its highest value when the buffer distance was 5 km, and their quantitative relationships be described by a stepwise regression equation: CCO2=0.32CISA-0.89CVeg+445.13 (R2 =0.66, P<0.01). PMID:26710641

  6. Structural Properties of Amorphous Indium-Based Oxides

    NASA Astrophysics Data System (ADS)

    Khanal, Rabi; Medvedeva, Julia

    2014-03-01

    Amorphous transparent conducting and semiconducting oxides exhibit similar or even superior properties to those observed in their crystalline counterparts. To understand how the structural properties change upon amorphization and how chemical composition affects the local and long-range structure of the amorphous oxides, we employ first-principles molecular dynamics to generate amorphous In-X-O with X =Zn, Ga, Sn, Ge, Y, or Sc, and compare their local structure features to those obtained for amorphous and crystalline indium oxide. The results reveal that the short-range structure of the Metal-O polyhedra is generally preserved in the amorphous oxides; however, different metals (In and X) show quantitatively or qualitatively different behavior. Some of the metals retain their natural distances and/or coordination; while others allow for a highly distorted environment and thus favor ``defect'' formation under variable oxygen conditions. At the same time, we find that the presence of X increases both the average In-O coordination and the number of the 6-coordinated In atoms as compared to those in IO. The improved In coordination may be responsible for the observed reduction in the carrier concentration as the substitution level in In-X-O increases.

  7. The relationship between pulmonary function tests, thorax HRCT, and quantitative ventilation-perfusion scintigraphy in chronic obstructive pulmonary disease.

    PubMed

    Demir, Tunçalp; Ikitimur, Hande; Akpinar Tekgündüz, Sibel; Mutlu, Birsen; Yildirim, Nurhayat; Akman, Canan; Ozmen, Ozlem; Kanmaz, Bedii

    2005-01-01

    We have evaluated the relationship between pulmonary function tests (PFT), thorax high resolution computed tomography (HRCT) images and quantitative ventilation-perfusion (V/Q) scintigraphic studies in 16 male patients (mean age 65.6 +/- 5.5 years) with chronic obstructive pulmonary disease (COPD). The mean forced vital capacity (FVC) value of the patient group was 2352 +/- 642 mL (65.4 +/- 15.8%), whereas mean forced expiratory volume in one second (FEV(1)) was found to be 1150 +/- 442 mL (40.8 +/- 14.9%). The ratio of carbon monoxide diffusion capacity to alveolar ventilation (DLCO/VA) was 3.17 +/- 0.88 mL/min/mmHg/L, and the mean partial oxygen (PaO(2)) and carbon dioxide (PaCO(2)) pressures were 68.5 +/- 11.04 mmHg and 38.9 +/- 5.8 mmHg respectively. For each patient, thorax HRCT and V/Q scintigraphic images of both lungs were divided into upper, mid and lower zones during examination. Visual scoring for the assessment of emphysema on thorax HRCT were used and images were graded from mild to severe (< or = 25% - > or = 76%). Emphysema scores were found to be higher on upper zones with accompanying lowest V/Q ratios. DLCO/VA, DLCO, total emphysema scores, and individual emphysema scores of the upper, mid and lower zones were found to be correlated. As a conclusion, it can be stated that emphysematous changes in COPD patients are more apparent in the upper lung zones, which also have the lowest V/Q ratios. PMID:16456733

  8. A novel quantitative structure-activity relationship model for prediction of biomagnification factor of some organochlorine pollutants.

    PubMed

    Fatemi, Mohammad Hossein; Baher, Elham

    2009-08-01

    The biomagnification factor (BMF) is an important property for toxicology and environmental chemistry. In this work, quantitative structure-activity relationship (QSAR) models were used for the prediction of BMF for a data set including 30 polychlorinated biphenyls and 12 organochlorine pollutants. This set was divided into training and prediction sets. The result of diversity test reveals that the structure of the training and test sets can represent those of the whole ones. After calculation and screening of a large number of molecular descriptors, the methods of stepwise multiple linear regression and genetic algorithm (GA) were used for the selection of most important and significant descriptors which were related to BMF. Then multiple linear regression and artificial neural network (ANN) techniques were applied as linear and non-linear feature mapping techniques, respectively. By comparison between statistical parameters of these methods it was concluded that an ANN model, which used GA selected descriptors, was superior over constructed models. Descriptors which were used by this model are: topographic electronic index, complementary information content, XY shadow/XY rectangle and difference between partial positively and negatively charge surface area. The standard errors for training and test sets of this model are 0.03 and 0.20, respectively. The degree of importance of each descriptor was evaluated by sensitivity analysis approach for the nonlinear model. A good results (Q (2) = 0.97 and SPRESS = 0.084) is obtained by applying cross-validation test that indicating the validation of descriptors in the obtained model in prediction of BMF for these compounds. PMID:19219557

  9. Rational Quantitative Structure-Activity Relationship (RQSAR) Screen for PXR and CAR Isoform-Specific Nuclear Receptor Ligands

    PubMed Central

    Dring, Ann M.; Anderson, Linnea E.; Qamar, Saima; Stoner, Matthew A.

    2010-01-01

    Constitutive androstane receptor (CAR) and pregnane X receptor (PXR) are closely related orphan nuclear receptor proteins that share several ligands and target overlapping sets of genes involved in homeostasis and all phases of drug metabolism. CAR and PXR are involved in the development of certain diseases, including diabetes, metabolic syndrome and obesity. Ligand screens for these receptors so far have typically focused on steroid hormone analogs with pharmacophore-based approaches, only to find relatively few new hits. Multiple CAR isoforms have been detected in human liver, with the most abundant being the constitutively active reference, CAR1, and the ligand-dependent isoform CAR3. It has been assumed that any compound that binds CAR1 should also activate CAR3, and so CAR3 can be used as a ligand-activated surrogate for CAR1 studies. The possibility of CAR3-specific ligands has not, so far, been addressed. To investigate the differences between CAR1, CAR3 and PXR, and to look for more CAR ligands that may be of use in quantitative structure-activity relationship (QSAR) studies, we performed a luciferase transactivation assay screen of 60 mostly non-steroid compounds. Known active compounds with different core chemistries were chosen as starting points and structural variants were rationally selected for screening. Distinct differences in agonist versus inverse agonist/antagonist effects were seen in 49 compounds that had some ligand effect on at least one receptor and 18 that had effects on all three receptors; eight were CAR1 ligands only, three were CAR3 only ligands and four affected PXR only. This work provides evidence for new CAR ligands, some of which have CAR3-specific effects, and provides observational data on CAR and PXR ligands with which to inform in silico strategies. Compounds that demonstrated unique activity on any one receptor are potentially valuable diagnostic tools for the investigation of in vivo molecular targets. PMID:20869355

  10. Development of acute toxicity quantitative structure activity relationships (QSAR) and their use in linear alkylbenzene sulfonate species sensitivity distributions.

    PubMed

    Belanger, Scott E; Brill, Jessica L; Rawlings, Jane M; Price, Brad B

    2016-07-01

    Linear Alkylbenzene Sulfonate (LAS) is high tonnage and widely dispersed anionic surfactant used by the consumer products sector. A range of homologous structures are used in laundry applications that differ primarily on the length of the hydrophobic alkyl chain. This research summarizes the development of a set of acute toxicity QSARs (Quantitative Structure Activity Relationships) for fathead minnows (Pimephales promelas) and daphnids (Daphnia magna, Ceriodaphnia dubia) using accepted test guideline approaches. A series of studies on pure chain length LAS from C10 to C14 were used to develop the QSARs and the robustness of the QSARs was tested by evaluation of two technical mixtures of differing compositions. All QSARs were high quality (R(2) were 0.965-0.997, p < 0.0001). Toxicity normalization employing QSARs is used to interpret a broader array of tests on LAS chain length materials to a diverse group of test organisms with the objective of developing Species Sensitivity Distributions (SSDs) for various chain lengths of interest. Mixtures include environmental distributions measured from exposure monitoring surveys of wastewater effluents, various commercial mixtures, or specific chain lengths. SSD 5th percentile hazardous concentrations (HC5s) ranged from 0.129 to 0.254 mg/L for wastewater effluents containing an average of 11.26-12 alkyl carbons. The SSDs are considered highly robust given the breadth of species (n = 19), use of most sensitive endpoints from true chronic studies and the quality of the underlying statistical properties of the SSD itself. The data continue to indicate a low hazard to the environment relative to expected environmental concentrations. PMID:27105149

  11. 4-Aminoquinolines Active against Chloroquine-Resistant Plasmodium falciparum: Basis of Antiparasite Activity and Quantitative Structure-Activity Relationship Analyses▿

    PubMed Central

    Hocart, Simon J.; Liu, Huayin; Deng, Haiyan; De, Dibyendu; Krogstad, Frances M.; Krogstad, Donald J.

    2011-01-01

    Chloroquine (CQ) is a safe and economical 4-aminoquinoline (AQ) antimalarial. However, its value has been severely compromised by the increasing prevalence of CQ resistance. This study examined 108 AQs, including 68 newly synthesized compounds. Of these 108 AQs, 32 (30%) were active only against CQ-susceptible Plasmodium falciparum strains and 59 (55%) were active against both CQ-susceptible and CQ-resistant P. falciparum strains (50% inhibitory concentrations [IC50s], ≤25 nM). All AQs active against both CQ-susceptible and CQ-resistant P. falciparum strains shared four structural features: (i) an AQ ring without alkyl substitution, (ii) a halogen at position 7 (Cl, Br, or I but not F), (iii) a protonatable nitrogen at position 1, and (iv) a second protonatable nitrogen at the end of the side chain distal from the point of attachment to the AQ ring via the nitrogen at position 4. For activity against CQ-resistant parasites, side chain lengths of ≤3 or ≥10 carbons were necessary but not sufficient; they were identified as essential factors by visual comparison of 2-dimensional (2-D) structures in relation to the antiparasite activities of the AQs and were confirmed by computer-based 3-D comparisons and differential contour plots of activity against P. falciparum. The advantage of the method reported here (refinement of quantitative structure-activity relationship [QSAR] descriptors by random assignment of compounds to multiple training and test sets) is that it retains QSAR descriptors according to their abilities to predict the activities of unknown test compounds rather than according to how well they fit the activities of the compounds in the training sets. PMID:21383099

  12. Assessment of quantitative structure-activity relationship of toxicity prediction models for Korean chemical substance control legislation

    PubMed Central

    Kim, Kwang-Yon; Shin, Seong Eun; No, Kyoung Tai

    2015-01-01

    Objectives For successful adoption of legislation controlling registration and assessment of chemical substances, it is important to obtain sufficient toxicological experimental evidence and other related information. It is also essential to obtain a sufficient number of predicted risk and toxicity results. Particularly, methods used in predicting toxicities of chemical substances during acquisition of required data, ultimately become an economic method for future dealings with new substances. Although the need for such methods is gradually increasing, the-required information about reliability and applicability range has not been systematically provided. Methods There are various representative environmental and human toxicity models based on quantitative structure-activity relationships (QSAR). Here, we secured the 10 representative QSAR-based prediction models and its information that can make predictions about substances that are expected to be regulated. We used models that predict and confirm usability of the information expected to be collected and submitted according to the legislation. After collecting and evaluating each predictive model and relevant data, we prepared methods quantifying the scientific validity and reliability, which are essential conditions for using predictive models. Results We calculated predicted values for the models. Furthermore, we deduced and compared adequacies of the models using the Alternative non-testing method assessed for Registration, Evaluation, Authorization, and Restriction of Chemicals Substances scoring system, and deduced the applicability domains for each model. Additionally, we calculated and compared inclusion rates of substances expected to be regulated, to confirm the applicability. Conclusions We evaluated and compared the data, adequacy, and applicability of our selected QSAR-based toxicity prediction models, and included them in a database. Based on this data, we aimed to construct a system that can be used

  13. Novel aliphatic lipid-based diesters for use in lubricant formulations: Structure property investigations

    NASA Astrophysics Data System (ADS)

    Raghunanan, Latchmi Cindy

    Structure-property relationships are increasingly valued for the identification of specifically engineered materials with properties optimized for targeted application(s). In this work, linear and branched diesters for use in lubricant formulations are prepared from lipid-based oleochemicals and their structure-property relationships reported. It is shown that the branched diesters possess exceptional physical property profiles, including suppression of crystallization, and are superior alternatives for use in lubricant formulations. For the linear aliphatic diesters, both high and low temperature properties were predictable functions of total chain length, and both were differently influenced by the fatty acid versus diol chain length. Symmetry did not influence either, although thermal stability decreased and thermal transition temperatures increased with increasing saturation. All of the linear diesters demonstrated Newtonian flow behaviour. Viscosity was also predictable as a function of total chain length; any microstructural features due to structural effects were superseded by mass effects.

  14. Structure-property study of keto-ether polyimides

    NASA Technical Reports Server (NTRS)

    Dezern, James F.; Croall, Catharine I.

    1991-01-01

    As part of an on-going effort to develop an understanding of how changes in the chemical structure affect polymer properties, an empirical study was performed on polyimides containing only ether and/or carbonyl connecting groups in the polymer backbone. During the past two decades the structure-property relationships in linear aromatic polyimides have been extensively investigated. More recently, work has been performed to study the effect of isomeric attachment of keto-ether polyimides on properties such as glass transition temperature and solubility. However, little work has been reported on the relation of polyimide structure to mechanical properties. The purpose of this study was to determine the effect of structural changes in the backbone of keto-ether polyimides on their mechanical properties, specifically, unoriented thin film tensile properties. This study was conducted in two stages. The purpose of the initial stage was to examine the physical and mechanical properties of a representative group (four) of polyimide systems to determine the optimum solvent and cure cycle requirements. These optimum conditions were then utilized in the second stage to prepare films of keto-ether polyimides which were evaluated for mechanical and physical properties. All of the polyimides were prepared using isomers of oxydianiline (ODA) and diaminobenzophenone (DABP) in combination with 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and 4,4'-oxydiphthalic anhydride (ODPA).

  15. Formation and structural properties of multi-block copolymer vesicles

    NASA Astrophysics Data System (ADS)

    Wang, Rong; Ma, Shiying

    2014-03-01

    Due to the unique structure, vesicles have attracted considerable attention for their potential applications, such as gene and drug delivery, microcapsules, nanoreactors, cell membrane mimetic, synthetic organelles, etc. By using dissipative particle dynamics, we studied the self-assembly of amphiphilic multi-block copolymer. The phase diagram was constructed by varying the interaction parameters and the composition of the block copolymers. The results show that the vesicles are stable in a large region which is different from the diblock copolymer or triblock copolymer. The structural properties of vesicles can be controlled by varying the interaction parameters and the length of the hydrophobic block. The relationship between the hydrophilic and hydrophobic block length vs the aqueous cavity size and vesicle size are revealed. The copolymers with shorter hydrophobic blocks length or the higher hydrophilicity are more likely to form vesicles with larger aqueous cavity size and vesicle size as well as thinner wall thickness. However, the increase in hydrophobic-block length results to form vesicles with smaller aqueous cavity size and larger vesicle size. Acknowledgments. This work has been supported by NNSFC (No. 21074053) and NBRPC (No. 2010CB923303).

  16. Quantitative structure-activity relationship study of antioxidative peptide by using different sets of amino acids descriptors

    NASA Astrophysics Data System (ADS)

    Li, Yao-Wang; Li, Bo; He, Jiguo; Qian, Ping

    2011-07-01

    A database consisting of 214 tripeptides which contain either His or Tyr residue was applied to study quantitative structure-activity relationships (QSAR) of antioxidative tripeptides. Partial Least-Squares Regression analysis (PLSR) was conducted using parameters individually of each amino acid descriptor, including Divided Physico-chemical Property Scores (DPPS), Hydrophobic, Electronic, Steric, and Hydrogen (HESH), Vectors of Hydrophobic, Steric, and Electronic properties (VHSE), Molecular Surface-Weighted Holistic Invariant Molecular (MS-WHIM), isotropic surface area-electronic charge index (ISA-ECI) and Z-scale, to describe antioxidative tripeptides as X-variables and antioxidant activities measured with ferric thiocyanate methods were as Y-variable. After elimination of outliers by Hotelling's T 2 method and residual analysis, six significant models were obtained describing the entire data set. According to cumulative squared multiple correlation coefficients ( R2), cumulative cross-validation coefficients ( Q2) and relative standard deviation for calibration set (RSD c), the qualities of models using DPPS, HESH, ISA-ECI, and VHSE descriptors are better ( R2 > 0.6, Q2 > 0.5, RSD c < 0.39) than that of models using MS-WHIM and Z-scale descriptors ( R2 < 0.6, Q2 < 0.5, RSD c > 0.44). Furthermore, the predictive ability of models using DPPS descriptor is best among the six descriptors systems (cumulative multiple correlation coefficient for predict set ( Rext2) > 0.7). It was concluded that the DPPS is better to describe the amino acid of antioxidative tripeptides. The results of DPPS descriptor reveal that the importance of the center amino acid and the N-terminal amino acid are far more than the importance of the C-terminal amino acid for antioxidative tripeptides. The hydrophobic (positively to activity) and electronic (negatively to activity) properties of the N-terminal amino acid are suggested to play the most important significance to activity, followed

  17. In Silico Quantitative Structure-Activity Relationship Studies on P-gp Modulators of Tetrahydroisoquinoline-Ethyl-Phenylamine Series

    PubMed Central

    2011-01-01

    Background Multidrug resistance (MDR) is a major obstacle in cancer chemotherapy. The drug efflux by a transport protein is the main reason for MDR. In humans, MDR mainly occurs when the ATP-binding cassette (ABC) family of proteins is overexpressed simultaneously. P-glycoprotein (P-gp) is most commonly associated with human MDR; it utilizes energy from adenosine triphosphate (ATP) to transport a number of substrates out of cells against concentration gradients. By the active transport of substrates against concentration gradients, intracellular concentrations of substrates are decreased. This leads to the cause of failure in cancer chemotherapy. Results Herein, we report Topomer CoMFA (Comparative Molecular Field Analysis) and HQSAR (Hologram Quantitative Structure Activity Relationship) models for third generation MDR modulators. The Topomer CoMFA model showed good correlation between the actual and predicted values for training set molecules. The developed model showed cross validated correlation coefficient (q2) = 0.536 and non-cross validated correlation coefficient (r2) = 0.975 with eight components. The best HQSAR model (q2 = 0.777, r2 = 0.956) with 5-8 atom counts was used to predict the activity of test set compounds. Both models were validated using test set compounds, and gave a good predictive values of 0.604 and 0.730. Conclusions The contour map near R1 indicates that substitution of a bulkier and polar group to the ortho position of the benzene ring enhances the inhibitory effect. This explains why compounds with a nitro group have good inhibitory potency. Molecular fragment analyses shed light on some essential structural and topological features of third generation MDR modulators. Fragments analysis showed that the presence of tertiary nitrogen, a central phenyl ring and an aromatic dimethoxy group contributed to the inhibitory effect. Based on contour map information and fragment information, five new molecules with variable R1 substituents were

  18. FISH ACUTE TOXICITY SYNDROMES AND THEIR USE IN THE QSAR (QUANTITATIVE STRUCTURE ACTIVITY RELATIONSHIP) APPROACH TO HAZARD ASSESSMENT

    EPA Science Inventory

    Implementation of the Toxic Substances Control Act of 1977 creates the need to reliably establish testing priorities because laboratory resources are limited and the number of industrial chemicals requiring evaluation is overwhelming. The use of quantitative structure activity re...

  19. Structural Properties of Defects in Glassy Liquids.

    PubMed

    Cubuk, Ekin D; Schoenholz, Samuel S; Kaxiras, Efthimios; Liu, Andrea J

    2016-07-01

    At zero temperature a disordered solid corresponds to a local minimum in the energy landscape. As the temperature is raised or the system is driven with a mechanical load, the system explores different minima via dynamical events in which particles rearrange their relative positions. We have shown recently that the dynamics of particle rearrangements are strongly correlated with a structural quantity associated with each particle, "softness", which we can identify using supervised machine learning. Particles of a given softness have a well-defined energy scale that governs local rearrangements; because of this property, softness greatly simplifies our understanding of glassy dynamics. Here we investigate the correlation of softness with other commonly used structural quantities, such as coordination number and local potential energy. We show that although softness strongly correlates with these properties, its predictive power for rearrangement dynamics is much higher. We introduce a useful metric for quantifying the quality of structural quantities as predictors of dynamics. We hope that, in the future, authors introducing new structural measures of dynamics will compare their proposals quantitatively to softness using this metric. We also show how softness correlations give insight into rearrangements. Finally, we explore the physical meaning of softness using unsupervised dimensionality reduction and reduced curve-fitting models, and show that softness can be recast in a form that is amenable to analytical treatment. PMID:27092716

  20. Quantitative Characterization of Surface Self-Assembly Imaging Using Shapelets

    NASA Astrophysics Data System (ADS)

    Abukhdeir, Nasser Mohieddin; Suderman, Robert; Lizotte, Daniel J.

    Microscopy and imaging of surface self-assembly phenomena have advanced significantly over the past decade. In order to determine structure/property relationships robust automated analysis of the resulting images is required, but has not advanced at an equally rapid pace. Recently, quantitative characterization techniques have been developed and applied, such as using bond-orientational order (BOO) theory. BOO-based methods have significant limitations in that they do not provide pixel-level resolution and are not robust in the presence of measurement noise. In this work, a fundamentally different method for automated quantitative characterization of surface self-assembly imaging is presented which uses a family of localized functions called ``shapelets''. The method is presented and applied to quantitative characterization of stripe and hexagonal patterns which are frequently observed in surface self-assembly. The shapelet-based method is shown to be general, highly accurate, and robust in the presence of measurement noise. It is able to efficiently determine local pattern characteristics such as pattern strength and orientation for the determination of structure/property relationships. This work was made possible by the Natural Sciences and Engineering Research Council of Canada and Compute Ontario.

  1. Receptor binding profiles and quantitative structure-affinity relationships of some 5-substituted-N,N-diallyltryptamines.

    PubMed

    Cozzi, Nicholas V; Daley, Paul F

    2016-02-01

    N,N-Diallyltryptamine (DALT) and 5-methoxy-N,N-diallyltryptamine (5-MeO-DALT) are two tryptamines synthesized and tested by Alexander Shulgin. In self-experiments, 5-MeO-DALT was reported to be psychoactive in the 12-20mg range, while the unsubstituted compound DALT had few discernible effects in the 42-80 mg range. Recently, 5-MeO-DALT has been used in nonmedical settings for its psychoactive effects, but these effects have been poorly characterized and little is known of its pharmacological properties. We extended the work of Shulgin by synthesizing additional 5-substituted-DALTs. We then compared them to DALT and 5-MeO-DALT for their binding affinities at 45 cloned receptors and transporter proteins. Based on in vitro binding affinity, we identified 27 potential receptor targets for the 5-substituted-DALT compounds. Five of the DALT compounds had affinity in the 10-80 nM range for serotonin 5-HT1A and 5-HT2B receptors, while the affinity of DALT itself at 5-HT1A receptors was slightly lower at 100 nM. Among the 5-HT2 subtypes, the weakest affinity was at 5-HT2A receptors, spanning 250-730 nM. Five of the DALT compounds had affinity in the 50-400 nM range for serotonin 5-HT1D, 5-HT6, and 5-HT7 receptors; again, it was the unsubstituted DALT that had the weakest affinity at all three subtypes. The test drugs had even weaker affinity for 5-HT1B, 5-HT1E, and 5-HT5A subtypes and little or no affinity for the 5-HT3 subtype. These compounds also had generally nanomolar affinities for adrenergic α2A, α2B, and α2C receptors, sigma receptors σ1 and σ2, histamine H1 receptors, and norepinephrine and serotonin uptake transporters. They also bound to other targets in the nanomolar-to-low micromolar range. Based on these binding results, it is likely that multiple serotonin receptors, as well as several nonserotonergic sites are important for the psychoactive effects of DALT drugs. To learn whether any quantitative structure-affinity relationships existed, we evaluated

  2. Molecular Modeling on Berberine Derivatives toward BuChE: An Integrated Study with Quantitative Structure-Activity Relationships Models, Molecular Docking, and Molecular Dynamics Simulations.

    PubMed

    Fang, Jiansong; Pang, Xiaocong; Wu, Ping; Yan, Rong; Gao, Li; Li, Chao; Lian, Wenwen; Wang, Qi; Liu, Ai-Lin; Du, Guan-Hua

    2016-05-01

    A dataset of 67 berberine derivatives for the inhibition of butyrylcholinesterase (BuChE) was studied based on the combination of quantitative structure-activity relationships models, molecular docking, and molecular dynamics methods. First, a series of berberine derivatives were reported, and their inhibitory activities toward butyrylcholinesterase (BuChE) were evaluated. By 2D- quantitative structure-activity relationships studies, the best model built by partial least-square had a conventional correlation coefficient of the training set (R(2) ) of 0.883, a cross-validation correlation coefficient (Qcv2) of 0.777, and a conventional correlation coefficient of the test set (Rpred2) of 0.775. The model was also confirmed by Y-randomization examination. In addition, the molecular docking and molecular dynamics simulation were performed to better elucidate the inhibitory mechanism of three typical berberine derivatives (berberine, C2, and C55) toward BuChE. The predicted binding free energy results were consistent with the experimental data and showed that the van der Waals energy term (ΔEvdw ) difference played the most important role in differentiating the activity among the three inhibitors (berberine, C2, and C55). The developed quantitative structure-activity relationships models provide details on the fine relationship linking structure and activity and offer clues for structural modifications, and the molecular simulation helps to understand the inhibitory mechanism of the three typical inhibitors. In conclusion, the results of this study provide useful clues for new drug design and discovery of BuChE inhibitors from berberine derivatives. PMID:26648584

  3. Quantitative structure activity relationship model for predicting the depletion percentage of skin allergic chemical substances of glutathione.

    PubMed

    Si, Hongzong; Wang, Tao; Zhang, Kejun; Duan, Yun-Bo; Yuan, Shuping; Fu, Aiping; Hu, Zhide

    2007-05-22

    A quantitative model was developed to predict the depletion percentage of glutathione (DPG) compounds by gene expression programming (GEP). Each kind of compound was represented by several calculated structural descriptors involving constitutional, topological, geometrical, electrostatic and quantum-chemical features of compounds. The GEP method produced a nonlinear and five-descriptor quantitative model with a mean error and a correlation coefficient of 10.52 and 0.94 for the training set, 22.80 and 0.85 for the test set, respectively. It is shown that the GEP predicted results are in good agreement with experimental ones, better than those of the heuristic method. PMID:17481417

  4. Improvement of radar quantitative precipitation estimation based on real-time adjustments to Z-R relationships and inverse distance weighting correction schemes

    NASA Astrophysics Data System (ADS)

    Wang, Gaili; Liu, Liping; Ding, Yuanyuan

    2012-05-01

    The errors in radar quantitative precipitation estimations consist not only of systematic biases caused by random noises but also spatially nonuniform biases in radar rainfall at individual rain-gauge stations. In this study, a real-time adjustment to the radar reflectivity-rainfall rates ( Z-R) relationship scheme and the gauge-corrected, radar-based, estimation scheme with inverse distance weighting interpolation was developed. Based on the characteristics of the two schemes, the two-step correction technique of radar quantitative precipitation estimation is proposed. To minimize the errors between radar quantitative precipitation estimations and rain gauge observations, a real-time adjustment to the Z-R relationship scheme is used to remove systematic bias on the time-domain. The gauge-corrected, radar-based, estimation scheme is then used to eliminate non-uniform errors in space. Based on radar data and rain gauge observations near the Huaihe River, the two-step correction technique was evaluated using two heavy-precipitation events. The results show that the proposed scheme improved not only in the underestimation of rainfall but also reduced the root-mean-square error and the mean relative error of radar-rain gauge pairs.

  5. Water solubility of selected C9-C18 alkanes using a slow-stir technique: Comparison to structure - property models.

    PubMed

    Letinski, Daniel J; Parkerton, Thomas F; Redman, Aaron D; Connelly, Martin J; Peterson, Brian

    2016-05-01

    Aqueous solubility is a fundamental physical-chemical substance property that strongly influences the distribution, fate and effects of chemicals upon release into the environment. Experimental water solubility was determined for 18 selected C9-C18 normal, branched and cyclic alkanes. A slow-stir technique was applied to obviate emulsion formation, which historically has resulted in significant overestimation of the aqueous solubility of such hydrophobic liquid compounds. Sensitive GC-MS based methods coupled with contemporary sample extraction techniques were employed to enable reproducible analysis of low parts-per billion aqueous concentrations. Water solubility measurements for most of the compounds investigated, are reported for the first time expanding available data for branched and cyclic alkanes. Measured water solubilities spanned four orders of magnitude ranging from 0.3 μg/L to 250 μg/L. Good agreement was observed for selected alkanes tested in this work and reported in earlier literature demonstrating the robustness of the slow-stir water solubility technique. Comparisons of measured alkane water solubilities were also made with those predicted by commonly used quantitative structure-property relationship models (e.g. SPARC, EPIWIN, ACD/Labs). Correlations are also presented between alkane measured water solubilities and molecular size parameters (e.g. molar volume, solvent accessible molar volume) affirming a mechanistic description of empirical aqueous solubility results and prediction previously reported for a more limited set of alkanes. PMID:26924078

  6. MOLECULAR TOPOLOGY AND NARCOSIS - A QUANTITATIVE STRUCTURE-ACTIVITY RELATIONSHIP (QSAR) STUDY OF ALCOHOLS USING COMPLEMENTARY INFORMATION CONTENT (CIC)

    EPA Science Inventory

    A newly formulated information -theoretic topological index - complementary information content (CIC) - defined for the planar chemical graph of molecules is applied in the QSAR studies of congeneric series of alcohols. Results show that CIC can quantitatively predict the LC50 va...

  7. Reduced short term memory in congenital adrenal hyperplasia (CAH) and its relationship to spatial and quantitative performance.

    PubMed

    Collaer, Marcia L; Hindmarsh, Peter C; Pasterski, Vickie; Fane, Briony A; Hines, Melissa

    2016-02-01

    Girls and women with classical congenital adrenal hyperplasia (CAH) experience elevated androgens prenatally and show increased male-typical development for certain behaviors. Further, individuals with CAH receive glucocorticoid (GC) treatment postnatally, and this GC treatment could have negative cognitive consequences. We investigated two alternative hypotheses, that: (a) early androgen exposure in females with CAH masculinizes (improves) spatial perception and quantitative abilities at which males typically outperform females, or (b) CAH is associated with performance decrements in these domains, perhaps due to reduced short-term-memory (STM). Adolescent and adult individuals with CAH (40 female and 29 male) were compared with relative controls (29 female and 30 male) on spatial perception and quantitative abilities as well as on Digit Span (DS) to assess STM and on Vocabulary to assess general intelligence. Females with CAH did not perform better (more male-typical) on spatial perception or quantitative abilities than control females, failing to support the hypothesis of cognitive masculinization. Rather, in the sample as a whole individuals with CAH scored lower on spatial perception (p ≤ .009), a quantitative composite (p ≤ .036), and DS (p ≤ .001), despite no differences in general intelligence. Separate analyses of adolescent and adult participants suggested the spatial and quantitative effects might be present only in adult patients with CAH; however, reduced DS performance was found in patients with CAH regardless of age group. Separate regression analyses showed that DS predicted both spatial perception and quantitative performance (both p ≤ .001), when age, sex, and diagnosis status were controlled. Thus, reduced STM in CAH patients versus controls may have more general cognitive consequences, potentially reducing spatial perception and quantitative skills. Although hyponatremia or other aspects of salt-wasting crises or additional hormone

  8. Ab initio predictions of the stability and structural properties of zincblende (III,TM)V magnetic semiconductor alloys

    NASA Astrophysics Data System (ADS)

    Caetano, C.; Pela, R. R.; Martini, S.; Marques, M.; Teles, L. K.

    2016-05-01

    First-principles calculations and statistical methods were combined to study electronic, magnetic, thermodynamic and structural properties of zincblende (III,Mn)V and (III,Cr)V magnetic semiconductor alloys, including both nitride and arsenide alloys. From phase diagrams it was observed that nitride alloys are much less stable than arsenide ones, although the former ones have more localized d-states at the Fermi level. It was observed that all alloys present an anisotropic behavior, with the strongest magnetic interaction in the < 110 > direction. The relationship between the structural properties of these alloys and their electronic and magnetic characteristics (i.e., their half-metallicity) was investigated.

  9. Quantitative relationship between potato tuber damage and counts of Pacific Coast wireworm (Coleoptera: Elateridae) in baits: seasonal effects.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Plots were baited with rolled oats in spring to assess the relationship between counts of Pacific coast wireworm, Limonius canus (Coleoptera: Elateridae) and damage to potato tubers. Baiting was done at 7 intervals beginning before planting of potatoes and ending following germination. Injury (per...

  10. QUANTITATIVE STRUCTURE-TOXICITY RELATIONSHIPS FOR A SERIES OF PRIMARY ALCOHOLS IN A MAMMALIAN VIRAL HOST CELL REACTIVATION ASSAY

    EPA Science Inventory

    Structure-toxicity relationships for alcohols in a wide variety of systems have been found to depend primarily on the effective molar concentration of alcohol that penetrates to a lipid site of action in the cell, and not on specific structural features. n contrast, a structure-a...

  11. Effect of wet grinding on structural properties of ball clay

    SciTech Connect

    Purohit, A. Chander, S.; Dhaka, M. S.; Hameed, A.; Singh, P.; Nehra, S. P.

    2015-05-15

    In this paper, the effect of wet grinding on structural properties of ball clay is undertaken. The wet grinding treatment was performed employing ball and vibro mills for different time spells of 2, 4, 8 and 16 hours. The structural properties were carried out using X-ray diffraction (XRD). The structure of ground samples is found to be simple cubic. The crystallographic parameters are calculated and slight change in lattice constant, inter planner spacing and particle size is observed with grinding treatment. The results are in agreement with the available literature.

  12. Quantitative structure-activity relationship of organosulphur compounds as soybean 15-lipoxygenase inhibitors using CoMFA and CoMSIA.

    PubMed

    Caballero, Julio; Fernández, Michael; Coll, Deysma

    2010-12-01

    Three-dimensional quantitative structure-activity relationship studies were carried out on a series of 28 organosulphur compounds as 15-lipoxygenase inhibitors using comparative molecular field analysis and comparative molecular similarity indices analysis. Quantitative information on structure-activity relationships is provided for further rational development and direction of selective synthesis. All models were carried out over a training set including 22 compounds. The best comparative molecular field analysis model only included steric field and had a good Q² = 0.789. Comparative molecular similarity indices analysis overcame the comparative molecular field analysis results: the best comparative molecular similarity indices analysis model also only included steric field and had a Q² = 0.894. In addition, this model predicted adequately the compounds contained in the test set. Furthermore, plots of steric comparative molecular similarity indices analysis field allowed conclusions to be drawn for the choice of suitable inhibitors. In this sense, our model should prove useful in future 15-lipoxygenase inhibitor design studies. PMID:21040497

  13. Why are there race/ethnic differences in adult body mass index–adiposity relationships? A quantitative critical review

    PubMed Central

    Heymsfield, S. B.; Peterson, C. M.; Thomas, D. M.; Heo, M.; Schuna, J. M.

    2016-01-01

    Summary Body mass index (BMI) is now the most widely used measure of adiposity on a global scale. Nevertheless, intense discussion centers on the appropriateness of BMI as a phenotypic marker of adiposity across populations differing in race and ethnicity. BMI-adiposity relations appear to vary significantly across race/ethnic groups, but a collective critical analysis of these effects establishing their magnitude and underlying body shape/composition basis is lacking. Accordingly, we systematically review the magnitude of these race-ethnic differences across non-Hispanic (NH) white, NH black and Mexican American adults, their anatomic body composition basis and potential biologically linked mechanisms, using both earlier publications and new analyses from the US National Health and Nutrition Examination Survey. Our collective observations provide a new framework for critically evaluating the quantitative relations between BMI and adiposity across groups differing in race and ethnicity; reveal new insights into BMI as a measure of adiposity across the adult age-span; identify knowledge gaps that can form the basis of future research and create a quantitative foundation for developing BMI-related public health recommendations. PMID:26663309

  14. Why are there race/ethnic differences in adult body mass index-adiposity relationships? A quantitative critical review.

    PubMed

    Heymsfield, S B; Peterson, C M; Thomas, D M; Heo, M; Schuna, J M

    2016-03-01

    Body mass index (BMI) is now the most widely used measure of adiposity on a global scale. Nevertheless, intense discussion centers on the appropriateness of BMI as a phenotypic marker of adiposity across populations differing in race and ethnicity. BMI-adiposity relations appear to vary significantly across race/ethnic groups, but a collective critical analysis of these effects establishing their magnitude and underlying body shape/composition basis is lacking. Accordingly, we systematically review the magnitude of these race-ethnic differences across non-Hispanic (NH) white, NH black and Mexican American adults, their anatomic body composition basis and potential biologically linked mechanisms, using both earlier publications and new analyses from the US National Health and Nutrition Examination Survey. Our collective observations provide a new framework for critically evaluating the quantitative relations between BMI and adiposity across groups differing in race and ethnicity; reveal new insights into BMI as a measure of adiposity across the adult age-span; identify knowledge gaps that can form the basis of future research and create a quantitative foundation for developing BMI-related public health recommendations. PMID:26663309

  15. Impact of observational incompleteness on the structural properties of protein interaction networks

    NASA Astrophysics Data System (ADS)

    Kuhnt, Mathias; Glauche, Ingmar; Greiner, Martin

    2007-01-01

    The observed structure of protein interaction networks is corrupted by many false positive/negative links. This observational incompleteness is abstracted as random link removal and a specific, experimentally motivated (spoke) link rearrangement. Their impact on the structural properties of gene-duplication-and-mutation network models is studied. For the degree distribution a curve collapse is found, showing no sensitive dependence on the link removal/rearrangement strengths and disallowing a quantitative extraction of model parameters. The spoke link rearrangement process moves other structural observables, like degree correlations, cluster coefficient and motif frequencies, closer to their counterparts extracted from the yeast data. This underlines the importance to take a precise modeling of the observational incompleteness into account when network structure models are to be quantitatively compared to data.

  16. Quantitative Use of Fluorescent In Situ Hybridization To Examine Relationships between Mycolic Acid-Containing Actinomycetes and Foaming in Activated Sludge Plants

    PubMed Central

    Davenport, Russell J.; Curtis, Thomas P.; Goodfellow, Michael; Stainsby, Fiona M.; Bingley, Marc

    2000-01-01

    The formation of viscous foams on aeration basins and secondary clarifiers of activated sludge plants is a common and widespread problem. Foam formation is often attributed to the presence of mycolic acid-containing actinomycetes (mycolata). In order to examine the relationship between the number of mycolata and foam, we developed a group-specific probe targeting the 16S rRNA of the mycolata, a protocol to permeabilize mycolata, and a statistically robust quantification method. Statistical analyses showed that a lipase-based permeabilization method was quantitatively superior to previously described methods (P << 0.05). When mixed liquor and foam samples were examined, most of the mycolata present were rods or cocci, although filamentous mycolata were also observed. A nested analysis of variance showed that virtually all of the measured variance occurred between fields of view and not between samples. On this basis we determined that as few as five fields of view could be used to give a statistically meaningful sample. Quantitative fluorescent in situ hybridization (FISH) was used to examine the relationship between foaming and the concentration of mycolata in a 20-m3 completely mixed activated sludge plant. Foaming occurred when the number of mycolata exceeded a certain threshold value. Baffling of the plant affected foaming without affecting the number of mycolata. We tentatively estimated that the threshold foaming concentration of mycolata was about 2 × 106 cells ml−1 or 4 × 1012 cells m−2. We concluded that quantitative use of FISH is feasible and that quantification is a prerequisite for rational investigation of foaming in activated sludge. PMID:10698786

  17. Quantitative structure-activity relationships of insecticides and plant growth regulators: comparative studies toward understanding the molecular mechanism of action.

    PubMed Central

    Iwamura, H; Nishimura, K; Fujita, T

    1985-01-01

    Emphasis was put on the comparative quantitative structure-activity approaches to the exploration of action mechanisms of structurally different classes of compounds showing the same type of activity as well as those of the same type of compounds having different actions. Examples were selected from studies performed on insecticides and plant growth regulators, i.e., neurotoxic carbamates, phosphates, pyrethroids and DDT analogs, insect juvenile hormone mimics, and cytokinin agonistic and antagonistic compounds. Similarities and dissimilarities in structures required to elicit activity between compounds classes were revealed in terms of physicochemical parameters, provoking further exploration and evoking insights into the molecular mechanisms of action which may lead to the development of new structures having better qualities. PMID:3905379

  18. A quantitative analysis of the relationship between an online homework system and student achievement in pre-calculus

    NASA Astrophysics Data System (ADS)

    Babaali, Parisa; Gonzalez, Lidia

    2015-07-01

    Supporting student success in entry-level mathematics courses at the undergraduate level has and continues to be a challenge. Recently we have seen an increased reliance on technological supports including software to supplement more traditional in-class instruction. In this paper, we explore the effects on student performance of the use of a computer software program to supplement instruction in an entry-level mathematics course at the undergraduate level, specifically, a pre-calculus course. Relying on data from multiple sections of the course over various semesters, we compare student performance in those classes utilizing the software against those in which it was not used. Quantitative analysis of the data then leads us to conclusions about the effectiveness of the software as well as recommendations for future iterations of the course and others like it.

  19. Validity of semi-quantitative scale for brain MRI in unilateral cerebral palsy due to periventricular white matter lesions: Relationship with hand sensorimotor function and structural connectivity

    PubMed Central

    Fiori, Simona; Guzzetta, Andrea; Pannek, Kerstin; Ware, Robert S.; Rossi, Giuseppe; Klingels, Katrijn; Feys, Hilde; Coulthard, Alan; Cioni, Giovanni; Rose, Stephen; Boyd, Roslyn N.

    2015-01-01

    Aim To provide first evidence of construct validity of a semi-quantitative scale for brain structural MRI (sqMRI scale) in children with unilateral cerebral palsy (UCP) secondary to periventricular white matter (PWM) lesions, by examining the relationship with hand sensorimotor function and whole brain structural connectivity. Methods Cross-sectional study of 50 children with UCP due to PWM lesions using 3 T (MRI), diffusion MRI and assessment of hand sensorimotor function. We explored the relationship of lobar, hemispheric and global scores on the sqMRI scale, with fractional anisotropy (FA), as a measure of brain white matter microstructure, and with hand sensorimotor measures (Assisting Hand Assessment, AHA; Jebsen–Taylor Test for Hand Function, JTTHF; Melbourne Assessment of Unilateral Upper Limb Function, MUUL; stereognosis; 2-point discrimination). Results Lobar and hemispheric scores on the sqMRI scale contralateral to the clinical side of hemiplegia correlated with sensorimotor paretic hand function measures and FA of a number of brain structural connections, including connections of brain areas involved in motor control (postcentral, precentral and paracentral gyri in the parietal lobe). More severe lesions correlated with lower sensorimotor performance, with the posterior limb of internal capsule score being the strongest contributor to impaired hand function. Conclusion The sqMRI scale demonstrates first evidence of construct validity against impaired motor and sensory function measures and brain structural connectivity in a cohort of children with UCP due to PWM lesions. More severe lesions correlated with poorer paretic hand sensorimotor function and impaired structural connectivity in the hemisphere contralateral to the clinical side of hemiplegia. The quantitative structural MRI scoring may be a useful clinical tool for studying brain structure–function relationships but requires further validation in other populations of CP. PMID:26106533

  20. Mass Spectrometry Based Identification of Geometric Isomers during Metabolic Stability Study of a New Cytotoxic Sulfonamide Derivatives Supported by Quantitative Structure-Retention Relationships

    PubMed Central

    Belka, Mariusz; Hewelt-Belka, Weronika; Sławiński, Jarosław; Bączek, Tomasz

    2014-01-01

    A set of 15 new sulphonamide derivatives, presenting antitumor activity have been subjected to a metabolic stability study. The results showed that besides products of biotransformation, some additional peaks occurred in chromatograms. Tandem mass spectrometry revealed the same mass and fragmentation pathway, suggesting that geometric isomerization occurred. Thus, to support this hypothesis, quantitative structure-retention relationships were applied. Human liver microsomes were used as an in vitro model of metabolism. The biotransformation reactions were tracked by liquid chromatography assay and additionally, fragmentation mass spectra were recorded. In silico molecular modeling at a semi-empirical level was conducted as a starting point for molecular descriptor calculations. A quantitative structure-retention relationship model was built applying multiple linear regression based on selected three-dimensional descriptors. The studied compounds revealed high metabolic stability, with a tendency to form hydroxylated biotransformation products. However, significant chemical instability in conditions simulating human body fluids was noticed. According to literature and MS data geometrical isomerization was suggested. The developed in sillico model was able to describe the relationship between the geometry of isomer pairs and their chromatographic retention properties, thus it supported the hypothesis that the observed pairs of peaks are most likely geometric isomers. However, extensive structural investigations are needed to fully identify isomers’ geometry. An effort to describe MS fragmentation pathways of novel chemical structures is often not enough to propose structures of potent metabolites and products of other chemical reactions that can be observed in compound solutions at early drug discovery studies. The results indicate that the relatively non-expensive and not time- and labor-consuming in sillico approach could be a good supportive tool assisting the

  1. Mass spectrometry based identification of geometric isomers during metabolic stability study of a new cytotoxic sulfonamide derivatives supported by quantitative structure-retention relationships.

    PubMed

    Belka, Mariusz; Hewelt-Belka, Weronika; Sławiński, Jarosław; Bączek, Tomasz

    2014-01-01

    A set of 15 new sulphonamide derivatives, presenting antitumor activity have been subjected to a metabolic stability study. The results showed that besides products of biotransformation, some additional peaks occurred in chromatograms. Tandem mass spectrometry revealed the same mass and fragmentation pathway, suggesting that geometric isomerization occurred. Thus, to support this hypothesis, quantitative structure-retention relationships were applied. Human liver microsomes were used as an in vitro model of metabolism. The biotransformation reactions were tracked by liquid chromatography assay and additionally, fragmentation mass spectra were recorded. In silico molecular modeling at a semi-empirical level was conducted as a starting point for molecular descriptor calculations. A quantitative structure-retention relationship model was built applying multiple linear regression based on selected three-dimensional descriptors. The studied compounds revealed high metabolic stability, with a tendency to form hydroxylated biotransformation products. However, significant chemical instability in conditions simulating human body fluids was noticed. According to literature and MS data geometrical isomerization was suggested. The developed in sillico model was able to describe the relationship between the geometry of isomer pairs and their chromatographic retention properties, thus it supported the hypothesis that the observed pairs of peaks are most likely geometric isomers. However, extensive structural investigations are needed to fully identify isomers' geometry. An effort to describe MS fragmentation pathways of novel chemical structures is often not enough to propose structures of potent metabolites and products of other chemical reactions that can be observed in compound solutions at early drug discovery studies. The results indicate that the relatively non-expensive and not time- and labor-consuming in sillico approach could be a good supportive tool assisting the

  2. Effect of temperature annealing on capacitive and structural properties of hydrous ruthenium oxides

    NASA Astrophysics Data System (ADS)

    Fang, Wei-Chuan; Huang, Jin-Hua; Chen, Li-Chyong; Su, Yuh-Long Oliver; Chen, Kuei-Hsien

    The structure-property relationships of hydrous ruthenium oxides, fabricated by electro deposition on Ti foil, were investigated with different annealing conditions. The annealing temperature was found to play an important role in affecting the electrochemical performance of the annealed hydrous ruthenium oxides. The results indicate that annealing hydrous ruthenium oxide at its crystallization threshold temperature, ∼200 °C, may help to create suitable nanostructure in the oxide that supports the establishment of interpenetrating percolation paths for balanced electron and proton conduction, thereby improving the capacitive response of the oxide dramatically. This finding is useful for fabrication of electrodes with enhanced electrochemical performance for application in microsupercapacitor.

  3. Perspective: Composition-structure-property mapping in high-throughput experiments: Turning data into knowledge

    NASA Astrophysics Data System (ADS)

    Hattrick-Simpers, Jason R.; Gregoire, John M.; Kusne, A. Gilad

    2016-05-01

    With their ability to rapidly elucidate composition-structure-property relationships, high-throughput experimental studies have revolutionized how materials are discovered, optimized, and commercialized. It is now possible to synthesize and characterize high-throughput libraries that systematically address thousands of individual cuts of fabrication parameter space. An unresolved issue remains transforming structural characterization data into phase mappings. This difficulty is related to the complex information present in diffraction and spectroscopic data and its variation with composition and processing. We review the field of automated phase diagram attribution and discuss the impact that emerging computational approaches will have in the generation of phase diagrams and beyond.

  4. Intracellular PK/PD Relationships of Free and Liposomal Doxorubicin: Quantitative Analyses and PK/PD Modeling.

    PubMed

    Soininen, Suvi K; Vellonen, Kati-Sisko; Heikkinen, Aki T; Auriola, Seppo; Ranta, Veli-Pekka; Urtti, Arto; Ruponen, Marika

    2016-04-01

    Nanomedicines are widely studied for intracellular delivery of cancer drugs. However, the relationship between intracellular drug concentrations and drug responses are poorly understood. In this study, cellular and nuclear concentrations of doxorubicin were quantified with LC/MS after cell exposure with free and liposomal doxorubicin (pH-sensitive and pegylated liposomes). Cellular uptake of pegylated liposomes was low (∼3-fold extracellular concentrations) compared with doxorubicin in free form and pH-sensitive liposomes (up to 280-fold extracellular concentrations) in rat glioma (BT4C) and renal clear cell carcinoma (Caki-2) cells. However, after the cell exposure with pegylated liposomes, intracellular doxorubicin was distributed into the nuclear compartment in both cell types. Despite high drug concentrations in the nuclei, Caki-2 cells showed strong resistance toward doxorubicin. A model was successfully built to describe PK/PD relationship between drug concentrations in nucleus and cytotoxic responses in BT4C cells. This model is the first step to link target site concentration of doxorubicin into its effect and can be a useful part of more comprehensive future in vivo PK/PD models. PMID:26950248

  5. A best​ comprehension about the toxicity of phenylsulfonyl carboxylates in Vibrio fischeri using quantitative structure activity/property relationship methods.

    PubMed

    de Melo, Eduardo Borges; Martins, João Paulo Athaíde; Miranda, Eduardo Hösel; Ferreira, Márcia Miguel Castro

    2016-03-01

    Aromatic sulfones comprise a class of chemicals used in agrochemical and pharmaceutical industries and as floatation and extractant agents in petrochemical and metallurgy industries. In this study, new QSA(P)R studies were carried out to predict the toxicity against Vibrio fischeri of a set of 52 aromatic sulfones. The same approach was used to evaluate the relationship between these endpoint and the water solubility, another important environmental endpoint. The study resulted in models of good statistical quality and mechanistic interpretation with a possible correlation between the two endpoints, but the toxic effect is also likely to depend on other physicochemical properties. The use of the PLS2, a method not commonly used in QSA(P)R studies, also produced models of greater reliability, and the relationship between the two endpoints was reinforced to some degree. These results are useful for better understanding the process by which these compounds exert their environmental toxicity, thus aiding in the development of industrially useful compounds with less potential environmental damage. PMID:26551227

  6. Using Linkage Analysis to Identify Quantitative Trait Loci for Sleep Apnea in Relationship to Body Mass Index

    PubMed Central

    PATEL, SR; ELSTON, RC; GRAY-MCGUIRE, C; ZHU, X; REDLINE, S

    2008-01-01

    Summary To understand the genetics of sleep apnea, we evaluated the relationship between the apnea hypopnea index (AHI) and body mass index (BMI) through linkage analysis to identify genetic loci that may influence AHI and BMI jointly and AHI independent of BMI. Haseman-Elston sibling regression was conducted on AHI, AHI adjusted for BMI and BMI in African-American and European-American pedigrees. A comparison of the magnitude of linkage peaks was used to assess the relationship between AHI and BMI. In EAs, the strongest evidence for linkage to AHI was on 6q23-25 and 10q24-q25, both decreasing after BMI adjustment, suggesting loci with pleiotropic effects. Also, a promising area of linkage to AHI but not BMI was observed on 6p11-q11 near the orexin-2 receptor, suggesting BMI independent pathways. In AAs the strongest evidence of linkage for AHI after adjusting for BMI was on chromosome 8p21.3 with linkage increasing after BMI adjustment and on 8q24.1 with linkage decreasing after BMI adjustment. Novel linkage peaks were also observed in AAs to both BMI and AHI on chromosome 13 near the serotonin-2a receptor. These analyses suggest genetic loci for sleep apnea that operate both independently of BMI and through BMI-related pathways. PMID:18754839

  7. Relationship between N2O Fluxes from an Almond Soil and Denitrifying Bacterial Populations Estimated by Quantitative PCR

    NASA Astrophysics Data System (ADS)

    Matiasek, M.; Suddick, E. C.; Smart, D. R.; Scow, K. M.

    2008-12-01

    Cultivated soils emit substantial quantities of nitrous oxide (N2O), a greenhouse gas with almost 300 times the radiative forcing potential of CO2. Agriculture-related activities generate from 6 to 35 Tg N2O-N per year, or about 60 to 70% of global production. The microbial processes of nitrification, denitrification and nitrifier denitrification are major biogenic sources of N2O to the atmosphere from soils. Denitrification is considered the major source of N2O especially when soils are wet. The microbial N transformations that produce N2O depend primarily on nitrogen (N) fertilizer, with water content, available carbon and soil temperature being secondary controllers. Despite the fact that microbial processes are responsible for N2O emissions, very little is known about the numbers or types of populations involved. The objective of this study was to relate changes in denitrifying population densities, using quantitative PCR (qPCR) of functional genes, to N2O emissions in a fertilized almond orchard. Quantitative PCR targeted three specific genes involved in denitrification: nirS, nirK and nosZ. Copy numbers of the genes were related back to population densities and the portion of organisms likely to produce nitrous oxide. The study site, a 21.7 acre almond orchard fitted with micro-sprinklers, was fertigated (irrigated and fertilized simultaneously) with 50 lbs/acre sodium nitrate in late March 2008, then irrigated weekly. Immediately after the initial fertigation, fluxes of N2O and CO2, moisture content, inorganic N and denitrification gene copy numbers were measured 6 times over 24 days. Despite the fact that N2O emissions increased following fertigation, there was no consistent increase in any of the targeted genes. The genes nirK and nirS ranged from 0.4-1.4 × 107 and 0.4-1.4 × 108, whereas nosZ ranged from 2-8 × 106 copy numbers per g soil, respectively. Considerable variation, compounded by the small sample sizes used for DNA analysis, made it difficult

  8. The relationship of quantitative epidermal growth factor receptor expression in non-small cell lung cancer to long term survival.

    PubMed Central

    Veale, D.; Kerr, N.; Gibson, G. J.; Kelly, P. J.; Harris, A. L.

    1993-01-01

    Increased expression of epidermal growth factor receptor (EGFr) has been reported in non small cell lung cancers (NSCLC) when compared to normal lung. We have examined post-operative survival in 19 surgically treated patients with NSCLC who had full characterisation of EGFr on primary tumour membrane preparations from resection specimens. There were ten squamous, seven adeno and two large cell carcinomas. The median concentration of high affinity sites was 31 fmol per mg of protein (4-1532) and the median dissociation constant (Kd) of these high affinity sites was 2.3 x 10(-10) per mol (1.2-30 x 10(-10)). Seven patients survived over 5 years. Twelve patients died between 8.5 and 55 months from the time of surgery. When > 5 year survivors were compared to non-survivors there was no difference as regards tumour size or stage, or as regards age or sex. The survivors had a median concentration of high affinity EGFr sites of 16.1 fmol mg-1 protein compared to a median concentration of 68.6 fmol mg-1 protein in the non-survivors (P = 0.01 Wilcoxon test). No long term survivor had > 35 fmol mg-1 protein of receptor. Thus EGFr quantitation may give independent prognostic information in NSCLC and help to select patients for adjuvant therapy after surgery. These results need confirmation in a larger prospective study. PMID:8391303

  9. Peroxisome induction potential and lipid-regulating activity in rats. Quantitative microscopy and chemical structure-activity relationships.

    PubMed Central

    McGuire, E. J.; Lucas, J. A.; Gray, R. H.; de la Iglesia, F. A.

    1991-01-01

    Structurally diverse lipid-regulating agents induce hepatomegaly, hepatic peroxisome proliferation, and hepatocarcinoma in rats by mechanisms not fully understood. Nevertheless the initial hepatic response is a prompt, florid proliferation of peroxisomes. In investigations reported here, changes in the rat hepatic peroxisome compartment were measured by quantitative microscopy to determine chemical structure requirements that relate to peroxisome proliferation and lipid regulation. Aryloxyalkanoic acids plus amide analogs, and thio, benzimidazole, phenylpiperazine, and oxazole derivatives induced peroxisome proliferation and generally decreased plasma triglyceride and total cholesterol levels. These compounds contain an acidic function or are readily metabolized to a chemical with an acidic function. Substitution of the acidic function with an adamantyloxy eliminated peroxisome proliferation and induced contrasting effects on lipid profile, increasing triglycerides and decreasing total cholesterol. A previously unreported, direct correlation emerged between peroxisome proliferation and plasma high-density lipoprotein-cholesterol levels. These effects could not be elicited separately, negating identification of functional groups that could be associated with either activity. Chemical structure and resulting peroxisome proliferation with changes in plasma lipoproteins are therefore closely interrelated in rats. Images Figure 1 PMID:1853935

  10. Quantitative assessment of aortic atherosclerosis in APOE*3 Leiden transgenic mice and its relationship to serum cholesterol exposure.

    PubMed

    Groot, P H; van Vlijmen, B J; Benson, G M; Hofker, M H; Schiffelers, R; Vidgeon-Hart, M; Havekes, L M

    1996-08-01

    Transgenic mice overexpressing the human dysfunctional apolipoprotein E variant, APOE*3 Leiden, develop hyperlipidemia and are highly susceptible to diet-induced atherosclerosis. In the present study, we investigated the effects of diet composition and feeding period on serum cholesterol exposure and the amount of atherosclerosis in the aortic sinus in these mice, using quantitative image analysis. On each of the three diets tested--a low-fat diet, a high-saturated-fat/cholesterol diet, and a high saturated-fat/high-cholesterol/0.5%-cholate diet--transgenic animals showed a marked hyperlipidemia compared with nontransgenic littermates. Measurement of the atherosclerotic lesion areas in cross sections of the aortic sinus in animals exposed to these three diets for up to 6 months showed a 5 to 10 times greater lesion area in transgenic mice compared with nontransgenic controls. Highly significant positive correlations were found between the log-transformed data on lesion area and serum cholesterol exposure (r = .82 to .85 for the 1-, 2-, and 3-month treatment groups), indicating that the hyperlipidemia is likely to be a major determinant in lesion formation. On the basis of these findings, we suggest that the APOE*3 Leiden mouse represents a promising model for intervention studies with hypolipidemic and antiatherosclerotic drugs. PMID:8696955

  11. Relationship between Peeled Internal Limiting Membrane Area and Anatomic Outcomes following Macular Hole Surgery: A Quantitative Analysis.

    PubMed

    Goker, Yasin Sakir; Koc, Mustafa; Yuksel, Kemal; Yazici, Ahmet Taylan; Demir, Abdulvahit; Gunes, Hasan; Ozpinar, Yavuz

    2016-01-01

    Purpose. To quantitatively evaluate the effects of peeled internal limiting membrane (ILM) area and anatomic outcomes following macular hole surgery using spectral domain optical coherence tomography (SD-OCT). Methods. Forty-one eyes in 37 consecutive patients with idiopathic, Gass stage 3-4 macular hole (MH) were enrolled in this retrospective comparative study. All patients were divided into 2 groups according to anatomic success or failure. Basal MH diameter, peeled ILM area, and MH height were calculated using SD-OCT. Other prognostic parameters, including age, stage, preoperative BCVA, and symptom duration were also assessed. Results. Thirty-two cases were classified as anatomic success, and 9 cases were classified as anatomic failure. Peeled ILM area was significantly wider and MH basal diameter was significantly less in the anatomic success group (p = 0.024 and 0.032, resp.). Other parameters did not demonstrate statistical significance. Conclusion. The findings of the present study show that the peeled ILM area can affect the anatomic outcomes of MH surgery. PMID:27413544

  12. Relationship between Peeled Internal Limiting Membrane Area and Anatomic Outcomes following Macular Hole Surgery: A Quantitative Analysis

    PubMed Central

    Goker, Yasin Sakir; Koc, Mustafa; Yuksel, Kemal; Yazici, Ahmet Taylan; Gunes, Hasan; Ozpinar, Yavuz

    2016-01-01

    Purpose. To quantitatively evaluate the effects of peeled internal limiting membrane (ILM) area and anatomic outcomes following macular hole surgery using spectral domain optical coherence tomography (SD-OCT). Methods. Forty-one eyes in 37 consecutive patients with idiopathic, Gass stage 3-4 macular hole (MH) were enrolled in this retrospective comparative study. All patients were divided into 2 groups according to anatomic success or failure. Basal MH diameter, peeled ILM area, and MH height were calculated using SD-OCT. Other prognostic parameters, including age, stage, preoperative BCVA, and symptom duration were also assessed. Results. Thirty-two cases were classified as anatomic success, and 9 cases were classified as anatomic failure. Peeled ILM area was significantly wider and MH basal diameter was significantly less in the anatomic success group (p = 0.024 and 0.032, resp.). Other parameters did not demonstrate statistical significance. Conclusion. The findings of the present study show that the peeled ILM area can affect the anatomic outcomes of MH surgery. PMID:27413544

  13. Theoretical Investigations and Density Functional Theory Based Quantitative Structure–Activity Relationships Model for Novel Cytotoxic Platinum(IV) Complexes

    PubMed Central

    2012-01-01

    Octahedral platinum(IV) complexes are promising candidates in the fight against cancer. In order to rationalize the further development of this class of compounds, detailed studies on their mechanisms of action, toxicity, and resistance must be provided and structure–activity relationships must be drawn. Herein, we report on theoretical and QSAR investigations of a series of 53 novel bis-, tris-, and tetrakis(carboxylato)platinum(IV) complexes, synthesized and tested for cytotoxicity in our laboratories. The hybrid DFT functional wb97x was used for optimization of the structure geometry and calculation of the descriptors. Reliable and robust QSAR models with good explanatory and predictive properties were obtained for both the cisplatin sensitive cell line CH1 and the intrinsically cisplatin resistant cell line SW480, with a set of four descriptors. PMID:23214999

  14. Three-dimensional quantitative structure-activity relationship study on anti-cancer activity of 3,4-dihydroquinazoline derivatives against human lung cancer A549 cells

    NASA Astrophysics Data System (ADS)

    Cho, Sehyeon; Choi, Min Ji; Kim, Minju; Lee, Sunhoe; Lee, Jinsung; Lee, Seok Joon; Cho, Haelim; Lee, Kyung-Tae; Lee, Jae Yeol

    2015-03-01

    A series of 3,4-dihydroquinazoline derivatives with anti-cancer activities against human lung cancer A549 cells were subjected to three-dimensional quantitative structure-activity relationship (3D-QSAR) studies using the comparative molecular similarity indices analysis (CoMSIA) approaches. The most potent compound, 1 was used to align the molecules. As a result, the best prediction was obtained with CoMSIA combined the steric, electrostatic, hydrophobic, hydrogen bond donor, and hydrogen bond acceptor fields (q2 = 0.720, r2 = 0.897). This model was validated by an external test set of 6 compounds giving satisfactory predictive r2 value of 0.923 as well as the scrambling stability test. This model would guide the design of potent 3,4-dihydroquinazoline derivatives as anti-cancer agent for the treatment of human lung cancer.

  15. Facile synthesis and quantitative structure-activity relationship study of antitumor active 2-(4-oxo-thiazolidin-2-ylidene)-3-oxo-propionitriles.

    PubMed

    Hanna, Mona Maurice; George, Riham François

    2012-01-01

    2-(5-Arylidene-4-oxo-3-phenyl-thiazolidin-2-ylidene)-3-oxo-propionitriles 4a-j were prepared via condensation of aromatic aldehydes with 4-thiazolidinones 3a,b. The latter was obtained via electrophilic attack of phenylisothiocyanate on 3-oxo-propionitriles 1a,b followed by reaction with chloroacetyl chloride under basic condition. Additionally, 2-(5-heteroalicyclic methylene) analogues 5a-h were prepared via Mannich reaction of the appropriate secondary amines and formaldehyde with 4-thiazolidinones 3a,b. Many of the synthesized compounds exhibited promising antitumor properties against colon HCT116 and breast T47D cell lines. 3D-Pharmacophore modeling and quantitative structure-activity relationship (QSAR) analysis were combined to explain the observed antitumor properties. PMID:22976330

  16. Inhibition of /sup 125/I-labeled ristocetin binding to Micrococcus luteus cells by the peptides related to bacterial cell wall mucopeptide precursors: quantitative structure-activity relationships

    SciTech Connect

    Kim, K.H.; Martin, Y.; Otis, E.; Mao, J.

    1989-01-01

    Quantitative structure-activity relationships (QSAR) of N-Ac amino acids, N-Ac dipeptides, and N-Ac tripeptides in inhibition of /sup 125/I-labeled ristocetin binding to Micrococcus luteus cell wall have been developed to probe the details of the binding between ristocetin and N-acetylated peptides. The correlation equations indicate that (1) the binding is stronger for peptides in which the side chain of the C-terminal amino acid has a large molar refractivity (MR) value, (2) the binding is weaker for peptides with polar than for those with nonpolar C-terminal side chains, (3) the N-terminal amino acid in N-Ac dipeptides contributes 12 times that of the C-terminal amino acid to binding affinity, and (4) the interactions between ristocetin and the N-terminal amino acid of N-acetyl tripeptides appear to be much weaker than those with the first two amino acids.

  17. QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis. [quantitative structure-activity relationship, complete neglect of differential overlap

    NASA Technical Reports Server (NTRS)

    Johnson, H.; Kenley, R. A.; Rynard, C.; Golub, M. A.

    1985-01-01

    Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of cationic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR-primeP(O)X, where R and R-prime are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrolysis rate constant.

  18. Structure-property relations and modeling of small crack fatigue behavior of various magnesium alloys

    NASA Astrophysics Data System (ADS)

    Bernard, Jairus Daniel

    Lightweight structural components are important to the automotive and aerospace industries so that better fuel economy can be realized. Magnesium alloys in particular are being examined to fulfill this need due to their attractive stiffness- and strength-to-weight ratios when compared to other materials. However, when introducing a material into new roles, one needs to properly characterize its mechanical properties. Fatigue behavior is especially important considering aerospace and automotive component applications. Therefore, quantifying the structure-property relationships and accurately predicting the fatigue behavior for these materials are vital. This study has two purposes. The first is to quantify the structure-property relationships for the fatigue behavior in an AM30 magnesium alloy. The second is to use the microstructural-based MultiStage Fatigue (MSF) model in order to accurately predict the fatigue behavior of three magnesium alloys: AM30, Elektron 21, and AZ61. While some studies have previously quantified the MSF material constants for several magnesium alloys, detailed research into the fatigue regimes, notably the microstructurally small crack (MSC) region, is lacking. Hence, the contribution of this work is the first of its kind to experimentally quantify the fatigue crack incubation and MSC regimes that are used for the MultiStage Fatigue model. Using a multi-faceted experimental approach, these regimes were explored with a replica method that used a dual-stage silicone based compound along with previously published in situ fatigue tests. These observations were used in calibrating the MultiStage Fatigue model.

  19. Structural Properties of Liquid SiC during Rapid Solidification

    PubMed Central

    Yan, WanJun; Gao, TingHong; Guo, XiaoTian; Qin, YunXiang; Xie, Quan

    2013-01-01

    The rapid solidification of liquid silicon carbide (SiC) is studied by molecular dynamic simulation using the Tersoff potential. The structural properties of liquid and amorphous SiC are analyzed by the radial distribution function, angular distribution function, coordination number, and visualization technology. Results show that both heteronuclear and homonuclear bonds exist and no atomic segregation occurs during solidification. The bond angles of silicon and carbon atoms are distributed at around 109° and 120°, respectively, and the average coordination number is <4. Threefold carbon atoms and fourfold silicon atoms are linked together by six typical structures and ultimately form a random network of amorphous structure. The simulated results help understand the structural properties of liquid and amorphous SiC, as well as other similar semiconductor alloys. PMID:24288474

  20. Structural properties of liquid SiC during rapid solidification.

    PubMed

    Yan, WanJun; Gao, TingHong; Guo, XiaoTian; Qin, YunXiang; Xie, Quan

    2013-01-01

    The rapid solidification of liquid silicon carbide (SiC) is studied by molecular dynamic simulation using the Tersoff potential. The structural properties of liquid and amorphous SiC are analyzed by the radial distribution function, angular distribution function, coordination number, and visualization technology. Results show that both heteronuclear and homonuclear bonds exist and no atomic segregation occurs during solidification. The bond angles of silicon and carbon atoms are distributed at around 109° and 120°, respectively, and the average coordination number is <4. Threefold carbon atoms and fourfold silicon atoms are linked together by six typical structures and ultimately form a random network of amorphous structure. The simulated results help understand the structural properties of liquid and amorphous SiC, as well as other similar semiconductor alloys. PMID:24288474

  1. PROS1 genotype phenotype relationships in a large cohort of adults with suspicion of inherited quantitative protein S deficiency.

    PubMed

    Alhenc-Gelas, Martine; Plu-Bureau, Genevieve; Horellou, Marie Hélène; Rauch, Antoine; Suchon, Pierre

    2016-02-29

    Inherited protein S deficiency (PSD) is an established risk factor for venous thromboembolism (VTE). However, data are conflicting concerning risk of VTE associated with decreased free PS level (FPS) and information on PROS1 genotype-phenotype relationship is sparse. In a retrospective cohort of 579 patients with inherited type I/III deficiency suspicion, PROS1 genotyping was performed and the effect of genotype on FPS and on VTE risk was investigated. We found 116 (including 65 novel) detrimental mutations (DM) in 222 (type I/III in 194, type II in 28), PS Heerlen in 74, possibly non DM in 38 and no mutation in 245 subjects. Among DMs, type I/IIIDMs only were found in subjects with FPS< 30 %. Prevalence of type I/III DM decreased with increasing FPS level. Risk of VT associated with FPS level and genotype was studied in the 467 subjects with personal or family history of thrombosis. Only type I/IIIDM carriers presented with an increased risk of VTE [1.41 (95 %CI (1.05-1.89)] compared to subjects with no mutation. Among the group of type I/IIIDM heterozygotes and subjects with no mutation, the optimal FPS cut-off point for identifying subjects at increased VTE risk was searched for. We found that only subjects with FPS< 30 % and type I/IIIDM presented with an increased risk [1.48 (95 %CI 1.08-2.04)]. Our findings confirm the value of a cut-off FPS level for identifying subjects at increased VTE risk far below the lower limit of the normal range and suggest a place for PROS1 genotyping in PSD diagnosis strategy. PMID:26466767

  2. Quantitative structure-retention relationships applied to development of liquid chromatography gradient-elution method for the separation of sartans.

    PubMed

    Golubović, Jelena; Protić, Ana; Otašević, Biljana; Zečević, Mira

    2016-04-01

    QSRR are mathematically derived relationships between the chromatographic parameters determined for a representative series of analytes in given separation systems and the molecular descriptors accounting for the structural differences among the investigated analytes. Artificial neural network is a technique of data analysis, which sets out to emulate the human brain's way of working. The aim of the present work was to optimize separation of six angiotensin receptor antagonists, so-called sartans: losartan, valsartan, irbesartan, telmisartan, candesartan cilexetil and eprosartan in a gradient-elution HPLC method. For this purpose, ANN as a mathematical tool was used for establishing a QSRR model based on molecular descriptors of sartans and varied instrumental conditions. The optimized model can be further used for prediction of an external congener of sartans and analysis of the influence of the analyte structure, represented through molecular descriptors, on retention behaviour. Molecular descriptors included in modelling were electrostatic, geometrical and quantum-chemical descriptors: connolly solvent excluded volume non-1,4 van der Waals energy, octanol/water distribution coefficient, polarizability, number of proton-donor sites and number of proton-acceptor sites. Varied instrumental conditions were gradient time, buffer pH and buffer molarity. High prediction ability of the optimized network enabled complete separation of the analytes within the run time of 15.5 min under following conditions: gradient time of 12.5 min, buffer pH of 3.95 and buffer molarity of 25 mM. Applied methodology showed the potential to predict retention behaviour of an external analyte with the properties within the training space. Connolly solvent excluded volume, polarizability and number of proton-acceptor sites appeared to be most influential paramateres on retention behaviour of the sartans. PMID:26838399

  3. Structural property of regulatory elements in human promoters

    NASA Astrophysics Data System (ADS)

    Cao, Xiao-Qin; Zeng, Jia; Yan, Hong

    2008-04-01

    The capacity of transcription factors to activate gene expression is encoded in the promoter sequences, which are composed of short regulatory motifs that function as transcription factor binding sites (TFBSs) for specific proteins. To the best of our knowledge, the structural property of TFBSs that controls transcription is still poorly understood. Rigidity is one of the important structural properties of DNA, and plays an important role in guiding DNA-binding proteins to the target sites efficiently. After analyzing the rigidity of 2897 TFBSs in 1871 human promoters, we show that TFBSs are generally more flexible than other genomic regions such as exons, introns, 3' untranslated regions, and TFBS-poor promoter regions. Furthermore, we find that the density of TFBSs is consistent with the average rigidity profile of human promoters upstream of the transcription start site, which implies that TFBSs directly influence the promoter structure. We also examine the local rigid regions probably caused by specific TFBSs such as the DNA sequence TATA(A/T)A(A/T) box, which may inhibit nucleosomes and thereby facilitate the access of transcription factors bound nearby. Our results suggest that the structural property of TFBSs accounts for the promoter structure as well as promoter activity.

  4. Quantitative structure–activity relationship study of P2X7 receptor inhibitors using combination of principal component analysis and artificial intelligence methods

    PubMed Central

    Ahmadi, Mehdi; Shahlaei, Mohsen

    2015-01-01

    P2X7 antagonist activity for a set of 49 molecules of the P2X7 receptor antagonists, derivatives of purine, was modeled with the aid of chemometric and artificial intelligence techniques. The activity of these compounds was estimated by means of combination of principal component analysis (PCA), as a well-known data reduction method, genetic algorithm (GA), as a variable selection technique, and artificial neural network (ANN), as a non-linear modeling method. First, a linear regression, combined with PCA, (principal component regression) was operated to model the structure–activity relationships, and afterwards a combination of PCA and ANN algorithm was employed to accurately predict the biological activity of the P2X7 antagonist. PCA preserves as much of the information as possible contained in the original data set. Seven most important PC's to the studied activity were selected as the inputs of ANN box by an efficient variable selection method, GA. The best computational neural network model was a fully-connected, feed-forward model with 7−7−1 architecture. The developed ANN model was fully evaluated by different validation techniques, including internal and external validation, and chemical applicability domain. All validations showed that the constructed quantitative structure–activity relationship model suggested is robust and satisfactory. PMID:26600858

  5. Quantitative Structure-Activity Relationship Analysis of the Effect of Metoclopramide and Related Compounds on the Surface Ionization of Fumed Silica.

    PubMed

    Buyuktimkin, Tuba; Wurster, Dale Eric

    2015-08-01

    Potentiometric titration curves were generated for fumed silica with various concentrations of dissolved metoclopramide. The effects of various benzamide analogs of metoclopramide, which are positively charged in the titration medium and differ solely by their aromatic substituents, as well as lidocaine, which is also structurally analogous but is mainly in the unionized form, were also studied. At sufficiently high pH, pH 7.0 and above, the silica surface charge was independent of the metoclopramide concentration. A reasonable linear relationship with a positive slope was found between the logarithmic octanol-water partition coefficient (log P) values of the compounds and the negative surface charge determined at pH 7.0 and 7.2. These results can be attributed to specific adsorbate-surface interactions rather than concentration effects. The carbonyl oxygens of the benzamide structures most likely form hydrogen bonds with the neutral silanols. The use of positively charged triethylamine and ephedrine resulted in surface charge values that were the least negative in the aforementioned quantitative structure-activity relationship analyses. These results are consistent with ionic interactions between the positively charged aliphatic amine groups and the negatively charged surface silanols occurring simultaneously with the nonionic interactions. PMID:26097011

  6. Quantitative relationships between huntingtin levels, polyglutamine length, inclusion body formation, and neuronal death provide novel insight into Huntington’s disease molecular pathogenesis

    PubMed Central

    Miller, Jason; Arrasate, Montserrat; Shaby, Benjamin A.; Mitra, Siddhartha; Masliah, Eliezer; Finkbeiner, Steven

    2010-01-01

    An expanded polyglutamine (polyQ) stretch in the protein huntingtin (htt) induces self-aggregation into inclusion bodies (IBs) and causes Huntington’s disease (HD). Defining precise relationships between early observable variables and neuronal death at the molecular and cellular levels should improve our understanding of HD pathogenesis. Here, we utilized an automated microscope that can track thousands of neurons individually over their entire lifetime to quantify interconnected relationships between early variables, such as htt levels, polyQ length, and IB formation, and neuronal death in a primary striatal model of HD. The resulting model revealed that: mutant htt increases the risk of death by tonically interfering with homeostatic coping mechanisms rather than producing accumulated damage to the neuron; htt toxicity is saturable; the rate limiting steps for inclusion body formation and death can be traced to different conformational changes in monomeric htt; and IB formation reduces the impact of a neuron’s starting levels of htt on its risk of death. Finally, the model that emerges from our quantitative measurements places critical limits on the potential mechanisms by which mutant htt might induce neurodegeneration, which should help direct future research. PMID:20685997

  7. Toxicity in relation to mode of action for the nematode Caenorhabditis elegans: Acute-to-chronic ratios and quantitative structure-activity relationships.

    PubMed

    Ristau, Kai; Akgül, Yeliz; Bartel, Anna Sophie; Fremming, Jana; Müller, Marie-Theres; Reiher, Luise; Stapela, Frederike; Splett, Jan-Paul; Spann, Nicole

    2015-10-01

    Acute-to-chronic ratios (ACRs) and quantitative structure-activity relationships (QSARs) are of particular interest in chemical risk assessment. Previous studies focusing on the relationship between the size or variation of ACRs to substance classes and QSAR models were often based on data for standard test organisms, such as daphnids and fish. In the present study, acute and chronic toxicity tests were performed with the nematode Caenorhabditis elegans for a total of 11 chemicals covering 3 substance classes (nonpolar narcotics: 1-propanol, ethanol, methanol, 2-butoxyethanol; metals: copper, cadmium, zinc; and carbamates: methomyl, oxamyl, aldicarb, dioxacarb). The ACRs were variable, especially for the carbamates and metals, although there was a trend toward small and less variable ACRs for nonpolar narcotic substances. The octanol-water partition coefficient was a good predictor for explaining acute and chronic toxicity of nonpolar narcotic substances to C. elegans, but not for carbamates. Metal toxicity could be related to the covalent index χm2r. Overall, the results support earlier results from ACR and QSAR studies with standard freshwater test animals. As such C. elegans as a representative of small soil/sediment invertebrates would probably be protected by risk assessment strategies already in use. To increase the predictive power of ACRs and QSARs, further research should be expanded to other species and compounds and should also consider the target sites and toxicokinetics of chemicals. PMID:25994998

  8. Quantitative structure-activity relationship study of P2X7 receptor inhibitors using combination of principal component analysis and artificial intelligence methods.

    PubMed

    Ahmadi, Mehdi; Shahlaei, Mohsen

    2015-01-01

    P2X7 antagonist activity for a set of 49 molecules of the P2X7 receptor antagonists, derivatives of purine, was modeled with the aid of chemometric and artificial intelligence techniques. The activity of these compounds was estimated by means of combination of principal component analysis (PCA), as a well-known data reduction method, genetic algorithm (GA), as a variable selection technique, and artificial neural network (ANN), as a non-linear modeling method. First, a linear regression, combined with PCA, (principal component regression) was operated to model the structure-activity relationships, and afterwards a combination of PCA and ANN algorithm was employed to accurately predict the biological activity of the P2X7 antagonist. PCA preserves as much of the information as possible contained in the original data set. Seven most important PC's to the studied activity were selected as the inputs of ANN box by an efficient variable selection method, GA. The best computational neural network model was a fully-connected, feed-forward model with 7-7-1 architecture. The developed ANN model was fully evaluated by different validation techniques, including internal and external validation, and chemical applicability domain. All validations showed that the constructed quantitative structure-activity relationship model suggested is robust and satisfactory. PMID:26600858

  9. Quantitative analysis of relationships between irradiation parameters and the reproducibility of cyclotron-produced (99m)Tc yields.

    PubMed

    Tanguay, J; Hou, X; Buckley, K; Schaffer, P; Bénard, F; Ruth, T J; Celler, A

    2015-05-21

    Cyclotron production of (99m)Tc through the (100)Mo(p,2n) (99m)Tc reaction channel is actively being investigated as an alternative to reactor-based (99)Mo generation by nuclear fission of (235)U. An exciting aspect of this approach is that it can be implemented using currently-existing cyclotron infrastructure to supplement, or potentially replace, conventional (99m)Tc production methods that are based on aging and increasingly unreliable nuclear reactors. Successful implementation will require consistent production of large quantities of high-radionuclidic-purity (99m)Tc. However, variations in proton beam currents and the thickness and isotopic composition of enriched (100)Mo targets, in addition to other irradiation parameters, may degrade reproducibility of both radionuclidic purity and absolute (99m)Tc yields. The purpose of this article is to present a method for quantifying relationships between random variations in production parameters, including (100)Mo target thicknesses and proton beam currents, and reproducibility of absolute (99m)Tc yields (defined as the end of bombardment (EOB) (99m)Tc activity). Using the concepts of linear error propagation and the theory of stochastic point processes, we derive a mathematical expression that quantifies the influence of variations in various irradiation parameters on yield reproducibility, quantified in terms of the coefficient of variation of the EOB (99m)Tc activity. The utility of the developed formalism is demonstrated with an example. We show that achieving less than 20% variability in (99m)Tc yields will require highly-reproducible target thicknesses and proton currents. These results are related to the service rate which is defined as the percentage of (99m)Tc production runs that meet the minimum daily requirement of one (or many) nuclear medicine departments. For example, we show that achieving service rates of 84.0%, 97.5% and 99.9% with 20% variations in target thicknesses requires producing on average

  10. Quantitative analysis of relationships between irradiation parameters and the reproducibility of cyclotron-produced 99mTc yields

    NASA Astrophysics Data System (ADS)

    Tanguay, J.; Hou, X.; Buckley, K.; Schaffer, P.; Bénard, F.; Ruth, T. J.; Celler, A.

    2015-05-01

    Cyclotron production of 99mTc through the 100Mo(p,2n) 99mTc reaction channel is actively being investigated as an alternative to reactor-based 99Mo generation by nuclear fission of 235U. An exciting aspect of this approach is that it can be implemented using currently-existing cyclotron infrastructure to supplement, or potentially replace, conventional 99mTc production methods that are based on aging and increasingly unreliable nuclear reactors. Successful implementation will require consistent production of large quantities of high-radionuclidic-purity 99mTc. However, variations in proton beam currents and the thickness and isotopic composition of enriched 100Mo targets, in addition to other irradiation parameters, may degrade reproducibility of both radionuclidic purity and absolute 99mTc yields. The purpose of this article is to present a method for quantifying relationships between random variations in production parameters, including 100Mo target thicknesses and proton beam currents, and reproducibility of absolute 99mTc yields (defined as the end of bombardment (EOB) 99mTc activity). Using the concepts of linear error propagation and the theory of stochastic point processes, we derive a mathematical expression that quantifies the influence of variations in various irradiation parameters on yield reproducibility, quantified in terms of the coefficient of variation of the EOB 99mTc activity. The utility of the developed formalism is demonstrated with an example. We show that achieving less than 20% variability in 99mTc yields will require highly-reproducible target thicknesses and proton currents. These results are related to the service rate which is defined as the percentage of 99mTc production runs that meet the minimum daily requirement of one (or many) nuclear medicine departments. For example, we show that achieving service rates of 84.0%, 97.5% and 99.9% with 20% variations in target thicknesses requires producing on average 1.2, 1.5 and 1.9 times the

  11. Application of a quantitative structure retention relationship approach for the prediction of the two-dimensional gas chromatography retention times of polycyclic aromatic sulfur heterocycle compounds.

    PubMed

    Gieleciak, Rafal; Hager, Darcy; Heshka, Nicole E

    2016-03-11

    Information on the sulfur classes present in petroleum is a key factor in determining the value of refined products and processing behavior in the refinery. A large part of the sulfur present is included in polycyclic aromatic sulfur heterocycles (PASHs), which in turn are difficult to desulfurize. Furthermore, some PASHs are potentially more mutagenic and carcinogenic than polycyclic aromatic hydrocarbons, PAHs. All of this calls for improved methods for the identification and quantification of individual sulfur species. Recent advances in analytical techniques such as comprehensive two-dimensional gas chromatography (GC×GC) have enabled the identification of many individual sulfur species. However, full identification of individual components, particularly in virgin oil fractions, is still out of reach as standards for numerous compounds are unavailable. In this work, a method for accurately predicting retention times in GC×GC using a QSRR (quantitative structure retention relationship) method was very helpful for the identification of individual sulfur compounds. Retention times for 89 saturated, aromatic, and polyaromatic sulfur-containing heterocyclic compounds were determined using two-dimensional gas chromatography. These retention data were correlated with molecular descriptors generated with CODESSA software. Two independent QSRR relationships were derived for the primary as well as the secondary retention characteristics. The predictive ability of the relationships was tested by using both independent sets of compounds and a cross-validation technique. When the corresponding chemical standards are unavailable, the equations developed for predicting retention times can be used to identify unknown chromatographic peaks by matching their retention times with those of sulfur compounds of known molecular structure. PMID:26879453

  12. Graph Theoretic Foundations of Multibody Dynamics Part I: Structural Properties.

    PubMed

    Jain, Abhinandan

    2011-06-21

    This is the first part of two papers that use concepts from graph theory to obtain a deeper understanding of the mathematical foundations of multibody dynamics. The key contribution is the development of a unifying framework that shows that key analytical results and computational algorithms in multibody dynamics are a direct consequence of structural properties and require minimal assumptions about the specific nature of the underlying multibody system. This first part focuses on identifying the abstract graph theoretic structural properties of spatial operator techniques in multibody dynamics. The second part paper exploits these structural properties to develop a broad spectrum of analytical results and computational algorithms.Towards this, we begin with the notion of graph adjacency matrices and generalize it to define block-weighted adjacency (BWA) matrices and their 1-resolvents. Previously developed spatial operators are shown to be special cases of such BWA matrices and their 1-resolvents. These properties are shown to hold broadly for serial and tree topology multibody systems. Specializations of the BWA and 1-resolvent matrices are referred to as spatial kernel operators (SKO) and spatial propagation operators (SPO). These operators and their special properties provide the foundation for the analytical and algorithmic techniques developed in the companion paper.We also use the graph theory concepts to study the topology induced sparsity structure of these operators and the system mass matrix. Similarity transformations of these operators are also studied. While the detailed development is done for the case of rigid-link multibody systems, the extension of these techniques to a broader class of systems (e.g. deformable links) are illustrated. PMID:22102790

  13. Determination of HART I Blade Structural Properties by Laboratory Testing

    NASA Technical Reports Server (NTRS)

    Jung, Sung N.; Lau, Benton H.

    2012-01-01

    The structural properties of higher harmonic Aeroacoustic Rotor Test (HART I) blades were measured using the original set of blades tested in the German-dutch wind tunnel (DNW) in 1994. the measurements include bending and torsion stiffness, geometric offsets, and mass and inertia properties of the blade. the measured properties were compared to the estimated values obtained initially from the blade manufacturer. The previously estimated blade properties showed consistently higher stiffness, up to 30 percent for the flap bending in the blade inboard root section.

  14. Structural properties of amorphous silicon produced by electron irradiation

    SciTech Connect

    Yamasaki, J.; Takeda, S.

    1999-07-01

    The structural properties of the amorphous Si (a-Si), which was created from crystalline silicon by 2 MeV electron irradiation at low temperatures about 25 K, are examined in detail by means of transmission electron microscopy and transmission electron diffraction. The peak positions in the radial distribution function (RDF) of the a-Si correspond well to those of a-Si fabricated by other techniques. The electron-irradiation-induced a-Si returns to crystalline Si after annealing at 550 C.

  15. Density Functional Study of the structural properties in Tamoxifen

    NASA Astrophysics Data System (ADS)

    de Coss-Martinez, Romeo; Tapia, Jorge A.; Quijano-Quiñones, Ramiro F.; Canto, Gabriel I.

    2013-03-01

    Using the density functional theory, we have studied the structural properties of Tamoxifen. The calculations were performed with two methodological approaches, which were implemented in SIESTA and Spartan codes. For SIESTA, we considerate a linear combination of atomic orbitals method, using pseudopotentials and the van der Waals approximation for the exchange-correlation potential. Here we analyzed and compared the atomic structure between our results and other theoretical study. We found differences in the bond lengths between the results, that could be attributed to code approaches in each one. This work was supported under Grant FOMIX 2011-09 N: 170297 of Ph.D. A. Tapia.

  16. RaptorX-Property: a web server for protein structure property prediction

    PubMed Central

    Wang, Sheng; Li, Wei; Liu, Shiwang; Xu, Jinbo

    2016-01-01

    RaptorX Property (http://raptorx2.uchicago.edu/StructurePropertyPred/predict/) is a web server predicting structure property of a protein sequence without using any templates. It outperforms other servers, especially for proteins without close homologs in PDB or with very sparse sequence profile (i.e. carries little evolutionary information). This server employs a powerful in-house deep learning model DeepCNF (Deep Convolutional Neural Fields) to predict secondary structure (SS), solvent accessibility (ACC) and disorder regions (DISO). DeepCNF not only models complex sequence–structure relationship by a deep hierarchical architecture, but also interdependency between adjacent property labels. Our experimental results show that, tested on CASP10, CASP11 and the other benchmarks, this server can obtain ∼84% Q3 accuracy for 3-state SS, ∼72% Q8 accuracy for 8-state SS, ∼66% Q3 accuracy for 3-state solvent accessibility, and ∼0.89 area under the ROC curve (AUC) for disorder prediction. PMID:27112573

  17. RaptorX-Property: a web server for protein structure property prediction.

    PubMed

    Wang, Sheng; Li, Wei; Liu, Shiwang; Xu, Jinbo

    2016-07-01

    RaptorX Property (http://raptorx2.uchicago.edu/StructurePropertyPred/predict/) is a web server predicting structure property of a protein sequence without using any templates. It outperforms other servers, especially for proteins without close homologs in PDB or with very sparse sequence profile (i.e. carries little evolutionary information). This server employs a powerful in-house deep learning model DeepCNF (Deep Convolutional Neural Fields) to predict secondary structure (SS), solvent accessibility (ACC) and disorder regions (DISO). DeepCNF not only models complex sequence-structure relationship by a deep hierarchical architecture, but also interdependency between adjacent property labels. Our experimental results show that, tested on CASP10, CASP11 and the other benchmarks, this server can obtain ∼84% Q3 accuracy for 3-state SS, ∼72% Q8 accuracy for 8-state SS, ∼66% Q3 accuracy for 3-state solvent accessibility, and ∼0.89 area under the ROC curve (AUC) for disorder prediction. PMID:27112573

  18. Exploring the quantitative relationship between metabolism and enzymatic phenotype by physiological modeling of glucose metabolism and lactate oxidation in solid tumors

    NASA Astrophysics Data System (ADS)

    Wang, Qian; Vaupel, Peter; Ziegler, Sibylle I.; Shi, Kuangyu

    2015-03-01

    Molecular imaging using PET or hyperpolarized MRI can characterize tumor phenotypes by assessing the related metabolism of certain substrates. However, the interpretation of the substrate turnover in terms of a pathophysiological understanding is not straightforward and only semiquantitative. The metabolism of imaging probes is influenced by a number of factors, such as the microvascular structure or the expression of key enzymes. This study aims to use computational simulation to investigate the relationship between the metabolism behind molecular imaging and the underlying tumor phenotype. The study focused on the pathways of glucose metabolism and lactate oxidation in order to establish the quantitative relationship between the expression of several transporters (GLUT, MCT1 and MCT4), expression of the enzyme hexokinase (HK), microvasculature and the metabolism of glucose or lactate and the extracellular pH distribution. A computational model for a 2D tumor tissue phantom was constructed and the spatio-temporal evolution of related species (e.g. oxygen, glucose, lactate, protons, bicarbonate ions) was estimated by solving reaction-diffusion equations. The proposed model was tested by the verification of the simulation results using in vivo and in vitro literature data. The influences of different expression levels of GLUT, MCT1, MCT4, HK and microvessel distribution on substrate concentrations were analyzed. The major results are consistent with experimental data (e.g. GLUT is more influential to glycolytic flux than HK; extracellular pH is not correlated with MCT expressions) and provide theoretical interpretation of the co-influence of multiple factors of the tumor microenvironment. This computational simulation may assist the generation of hypotheses to bridge the discrepancy between tumor metabolism and the functions of transporters and enzymes. It has the potential to accelerate the development of multi-modal imaging strategies for assessment of tumor

  19. Structural properties of impact ices accreted on aircraft structures

    NASA Technical Reports Server (NTRS)

    Scavuzzo, R. J.; Chu, M. L.

    1987-01-01

    The structural properties of ice accretions formed on aircraft surfaces are studied. The overall objectives are to measure basic structural properties of impact ices and to develop finite element analytical procedures for use in the design of all deicing systems. The Icing Research Tunnel (IRT) was used to produce simulated natural ice accretion over a wide range of icing conditions. Two different test apparatus were used to measure each of the three basic mechanical properties: tensile, shear, and peeling. Data was obtained on both adhesive shear strength of impact ices and peeling forces for various icing conditions. The influences of various icing parameters such as tunnel air temperature and velocity, icing cloud drop size, material substrate, surface temperature at ice/material interface, and ice thickness were studied. A finite element analysis of the shear test apparatus was developed in order to gain more insight in the evaluation of the test data. A comparison with other investigators was made. The result shows that the adhesive shear strength of impact ice typically varies between 40 and 50 psi, with peak strength reaching 120 psi and is not dependent on the kind of substrate used, the thickness of accreted ice, and tunnel temperature below 4 C.

  20. Synthesis, pharmacological characterization, and quantitative structure-activity relationship analyses of 3,7,9,9-tetraalkylbispidines: derivatives with specific bradycardic activity.

    PubMed

    Schön, U; Antel, J; Brückner, R; Messinger, J; Franke, R; Gruska, A

    1998-01-29

    A series of 3,7,9,9-tetraalkyl-3,7-diazabicyclo[3.3.1]nonane derivatives (bispidines) was synthesized and identified as potential antiischemic agents. Pharmacological experiments in vitro as well as in vivo are described, and the results are listed. For selection of those compounds fitting best to the desired profile of a specific bradycardic antianginal agent--decrease in heart rate without affecting contractility and blood pressure--these results were scored and ranked. Quantitative structure--activity relationship (QSAR) analyses were performed and discussed a posteriori by means of Hansch, nonelementary discriminant and factor analysis to get insight into the molecular features determining the biological profile. Highly significant equations were obtained, indicating hydrophobic and steric effects. Both pharmacological ranking and QSAR considerations showed compound 6 as the optimum within the structural class under investigation. Compound 6 (tedisamil, KC8857) has been selected as the most promising compound and was chosen for further pharmacological and clinical investigations as an antiischemic drug. PMID:9464363

  1. Three-dimensional quantitative structure–activity relationship and docking studies in a series of anthocyanin derivatives as cytochrome P450 3A4 inhibitors

    PubMed Central

    Shityakov, Sergey; Puskás, István; Roewer, Norbert; Förster, Carola; Broscheit, Jens

    2014-01-01

    The cytochrome P450 (CYP)3A4 enzyme affects the metabolism of most drug-like substances, and its inhibition may influence drug safety. Modulation of CYP3A4 by flavonoids, such as anthocyanins, has been shown to inhibit the mutagenic activity of mammalian cells. Considering the previous investigations addressing CYP3A4 inhibition by these substances, we studied the three-dimensional quantitative structure–activity relationship (3D-QSAR) in a series of anthocyanin derivatives as CYP3A4 inhibitors. For the training dataset (n=12), comparative molecular field analysis (CoMFA) and comparative molecular similarity index analysis (CoMSIA) yielded crossvalidated and non-crossvalidated models with a q2 of 0.795 (0.687) and r2 of 0.962 (0.948), respectively. The models were also validated by an external test set of four compounds with r2 of 0.821 (CoMFA) and r2 of 0.812 (CoMSIA). The binding affinity modes associated with experimentally derived IC50 (half maximal inhibitory concentration) values were confirmed by molecular docking into the CYP3A4 active site with r2 of 0.66. The results obtained from this study are useful for a better understanding of the effects of anthocyanin derivatives on inhibition of carcinogen activation and cellular DNA damage. PMID:24741320

  2. Towards cheminformatics-based estimation of drug therapeutic index: Predicting the protective index of anticonvulsants using a new quantitative structure-index relationship approach.

    PubMed

    Chen, Shangying; Zhang, Peng; Liu, Xin; Qin, Chu; Tao, Lin; Zhang, Cheng; Yang, Sheng Yong; Chen, Yu Zong; Chui, Wai Keung

    2016-06-01

    The overall efficacy and safety profile of a new drug is partially evaluated by the therapeutic index in clinical studies and by the protective index (PI) in preclinical studies. In-silico predictive methods may facilitate the assessment of these indicators. Although QSAR and QSTR models can be used for predicting PI, their predictive capability has not been evaluated. To test this capability, we developed QSAR and QSTR models for predicting the activity and toxicity of anticonvulsants at accuracy levels above the literature-reported threshold (LT) of good QSAR models as tested by both the internal 5-fold cross validation and external validation method. These models showed significantly compromised PI predictive capability due to the cumulative errors of the QSAR and QSTR models. Therefore, in this investigation a new quantitative structure-index relationship (QSIR) model was devised and it showed improved PI predictive capability that superseded the LT of good QSAR models. The QSAR, QSTR and QSIR models were developed using support vector regression (SVR) method with the parameters optimized by using the greedy search method. The molecular descriptors relevant to the prediction of anticonvulsant activities, toxicities and PIs were analyzed by a recursive feature elimination method. The selected molecular descriptors are primarily associated with the drug-like, pharmacological and toxicological features and those used in the published anticonvulsant QSAR and QSTR models. This study suggested that QSIR is useful for estimating the therapeutic index of drug candidates. PMID:27262528

  3. Cellular Quantitative Structure–Activity Relationship (Cell-QSAR): Conceptual Dissection of Receptor Binding and Intracellular Disposition in Antifilarial Activities of Selwood Antimycins

    PubMed Central

    2012-01-01

    We present the cellular quantitative structure–activity relationship (cell-QSAR) concept that adapts ligand-based and receptor-based 3D-QSAR methods for use with cell-level activities. The unknown intracellular drug disposition is accounted for by the disposition function (DF), a model-based, nonlinear function of a drug’s lipophilicity, acidity, and other properties. We conceptually combined the DF with our multispecies, multimode version of the frequently used ligand-based comparative molecular field analysis (CoMFA) method, forming a single correlation function for fitting the cell-level activities. The resulting cell-QSAR model was applied to the Selwood data on filaricidal activities of antimycin analogues. Their molecules are flexible, ionize under physiologic conditions, form different intramolecular H-bonds for neutral and ionized species, and cross several membranes to reach unknown receptors. The calibrated cell-QSAR model is significantly more predictive than other models lacking the disposition part and provides valuable structure optimization clues by factorizing the cell-level activity of each compound into the contributions of the receptor binding and disposition. PMID:22468611

  4. Drug interaction study of natural steroids from herbs specifically toward human UDP-glucuronosyltransferase (UGT) 1A4 and their quantitative structure activity relationship (QSAR) analysis for prediction.

    PubMed

    Xu, Min; Dong, Peipei; Tian, Xiangge; Wang, Chao; Huo, Xiaokui; Zhang, Baojing; Wu, Lijun; Deng, Sa; Ma, Xiaochi

    2016-08-01

    The wide application of herbal medicines and foods containing steroids has resulted in the high risk of herb-drug interactions (HDIs). The present study aims to evaluate the inhibition potential of 43 natural steroids from herb medicines toward human UDP- glucuronosyltransferases (UGTs). A remarkable structure-dependent inhibition toward UGT1A4 was observed in vitro. Some natural steroids such as gitogenin, tigogenin, and solasodine were found to be the novel selective inhibitors of UGT1A4, and did not inhibit the activities of major human CYP isoforms. To clarify the possibility of the in vivo interaction of common steroids and clinical drugs, the kinetic inhibition type and related kinetic parameters (Ki) were measured. The target compounds 2-6 and 15, competitively inhibited the UGT1A4-catalyzed trifluoperazine glucuronidation reaction, with Ki values of 0.6, 0.18, 1.1, 0.7, 0.8, and 12.3μM, respectively. And this inhibition of steroids towards UGT1A4 was also verified in human primary hepatocytes. Furthermore, a quantitative structure-activity relationship (QSAR) of steroids with inhibitory effects toward human UGT1A4 isoform was established using the computational methods. Our findings elucidate the potential for in vivo HDI effects of steroids in herbal medicine and foods, with the clinical dr ugs eliminated by UGT1A4, and reveal the vital pharamcophoric requirement of natural steroids for UGT1A4 inhibition activity. PMID:27208893

  5. Physicochemical explanation of peptide binding to HLA-A*0201 major histocompatibility complex: a three-dimensional quantitative structure-activity relationship study.

    PubMed

    Doytchinova, Irini A; Flower, Darren R

    2002-08-15

    A three-dimensional quantitative structure-activity relationship method for the prediction of peptide binding affinities to the MHC class I molecule HLA-A*0201 was developed by applying the CoMSIA technique on a set of 266 peptides. To increase the self consistency of the initial CoMSIA model, the poorly predicted peptides were excluded from the training set in a stepwise manner and then included in the study as a test set. The final model, based on 236 peptides and considering the steric, electrostatic, hydrophobic, hydrogen bond donor, and hydrogen bond acceptor fields, had q2 = 0.683 and r2 = 0.891. The stability of this model was proven by cross-validations in two and five groups and by a bootstrap analysis of the non-cross-validated model. The residuals between the experimental pIC50 (-logIC50) values and those calculated by "leave-one-out" cross-validation were analyzed. According to the best model, 63.2% of the peptides were predicted with /residuals/ < or = 0.5 log unit; 29.3% with 1.0 < or = /residuals/ < 0.5; and 7.5% with /residuals/ > 1.0 log unit. The mean /residual/ value was 0.489. The coefficient contour maps identify the physicochemical property requirements at each position in the peptide molecule and suggest amino acid sequences for high-affinity binding to the HLA-A*0201 molecule. PMID:12112675

  6. Binding studies and quantitative structure-activity relationship of 3-amino-1H-indazoles as inhibitors of GSK3β.

    PubMed

    Caballero, Julio; Zilocchi, Szymon; Tiznado, William; Collina, Simona; Rossi, Daniela

    2011-10-01

    Docking of 3-amino-1H-indazoles complexed with glycogen synthase kinase 3 beta (GSK3β) was performed to gain insight into the structural requirements and preferred conformations of these inhibitors. The study was conducted on a selected set of 57 compounds with variation in structure and activity. We found that the most active compounds established three hydrogen bonds with the residues of the hinge region of GSK3β, but some of the less active compounds have other binding modes. In addition, models able to predict GSK3β inhibitory activities (IC(50) ) of the studied compounds were obtained by 3D-QSAR methods CoMFA and CoMSIA. Ligand-based and receptor-guided alignment methods were utilized. Adequate R(2) and Q(2) values were obtained by each method, although some striking differences existed between the obtained contour maps. Each of the predictive models exhibited a similar ability to predict the activity of a test set. The application of docking and quantitative structure-activity relationship together allowed conclusions to be drawn for the choice of suitable GSK3β inhibitors. PMID:21756288

  7. Quantitative structure-retention relationships applied to liquid chromatography gradient elution method for the determination of carbonyl-2,4-dinitrophenylhydrazone compounds.

    PubMed

    Cirera-Domènech, Elisenda; Estrada-Tejedor, Roger; Broto-Puig, Francesc; Teixidó, Jordi; Gassiot-Matas, Miquel; Comellas, Lluís; Lliberia, Josep Lluís; Méndez, Alberto; Paz-Estivill, Susanna; Delgado-Ortiz, Maria Rosa

    2013-02-01

    A usual method for the determination of aldehydes and ketones in different matrices consists of a derivatization with 2,4-dinitrophenylhydrazine (DNPH) followed by HPLC-UV analysis. In the present work, a HPLC-UV gradient elution method has been applied to the analysis of 13 aldehydes and ketones-DNPH in automotive emission samples. In addition to these 13 compounds-DNPH, several carbonyl-DNPH compounds (linear, ramified and cyclic, saturated and unsaturated compounds) have been analyzed by HPLC-UV. Quantitative structure-retention relationships (QSRR) methods have been applied to predict the logarithm of capacity factor (logk') of carbonyl-DNPH compounds. According to its physicochemical meaning, combinations of 2 and 3 molecular descriptors have been proposed in order to achieve higher correlation with logk'. Using linear and non-linear QSRR methodologies, the resulting prediction models allowed the screening of the most probable carbonyl-DNPH derivative candidates that correspond to unknown compounds detected in automotive emission samples. This information has been useful for their identification by UPLC(®)-MS/MS. In addition, the chromatographic retention of different carbonyl-DNPH compound families was studied using two HPLC isocratic methods working with two orthogonal stationary phases (octadecylpolyethoxysilane and cyanopropyl). Differences between the retention indexes obtained for each column were used for classifying carbonyl-DNPH into compounds families. PMID:23298845

  8. Three-dimensional quantitative structure-activity relationships and docking studies of some structurally diverse flavonoids and design of new aldose reductase inhibitors

    PubMed Central

    Chandra De, Utpal; Debnath, Tanusree; Sen, Debanjan; Debnath, Sudhan

    2015-01-01

    Aldose reductase (AR) plays an important role in the development of several long-term diabetic complications. Inhibition of AR activities is a strategy for controlling complications arising from chronic diabetes. Several AR inhibitors have been reported in the literature. Flavonoid type compounds are shown to have significant AR inhibition. The objective of this study was to perform a computational work to get an idea about structural insight of flavonoid type compounds for developing as well as for searching new flavonoid based AR inhibitors. The data-set comprising 68 flavones along with their pIC50 values ranging from 0.44 to 4.59 have been collected from literature. Structure of all the flavonoids were drawn in Chembiodraw Ultra 11.0, converted into corresponding three-dimensional structure, saved as mole file and then imported to maestro project table. Imported ligands were prepared using LigPrep option of maestro 9.6 version. Three-dimensional quantitative structure-activity relationships and docking studies were performed with appropriate options of maestro 9.6 version installed in HP Z820 workstation with CentOS 6.3 (Linux). A model with partial least squares factor 5, standard deviation 0.2482, R2 = 0.9502 and variance ratio of regression 122 has been found as the best statistical model. PMID:25709964

  9. Degradation mechanism of PCDDs initiated by OH radical in Photo-Fenton oxidation technology: quantum chemistry and quantitative structure-activity relationship.

    PubMed

    Sun, Xiaomin; Sun, Tingli; Zhang, Qingzhu; Wang, Wenxing

    2008-08-25

    A detailed understanding of the degradation mechanism of polychlorinated dibenzo-p-dioxins (PCDDs) is of great necessity. In wastewater treatment, an important degradation process of PCDDs ascribes to its reaction with the photo-Fenton reagent. In this paper, the reaction of 2,3,7,8-TeCDD with OH radicals has been studied using high level molecular orbital theory. The profile of the potential energy surface is constructed. A complete description of the possible degradation mechanism in solution is provided. Two degradation mechanisms are proposed: ring-opening and adducting mechanism, adducting and ring-opening mechanism. The main products obtained are 4,5-dichlorinate-o-dihydroxybenzene and 4,5-dichlorinate-o-quinone. The study on the quantitative structure-activity relationship of these PCDDs is performed. The structure-activity model has been constructed, in which three structural parameters, RO5-C12, RO5-C13 and QC14, are found to be positively correlated to the degradation activities. PMID:18554686

  10. Synthesis and quantitative structure-activity relationship (QSAR) study of novel 4-acyloxypodophyllotoxin derivatives modified in the A and C rings as insecticidal agents.

    PubMed

    He, Shuzhen; Shao, Yonghua; Fan, Lingling; Che, Zhiping; Xu, Hui; Zhi, Xiaoyan; Wang, Juanjuan; Yao, Xiaojun; Qu, Huan

    2013-01-23

    In continuation of our program aimed at the discovery and development of natural-product-based insecticidal agents, we have synthesized three series of novel 4-acyloxy compounds derived from podophyllotoxin modified in the A and C rings, which is isolated as the main secondary metabolite from the roots and rhizomes of Podophyllum hexandrum . Their insecticidal activity was preliminarily evaluated against the pre-third-instar larvae of Mythimna separata in vivo. Compound 9g displayed the best promising insecticidal activity. It revealed that cleavage of the 6,7-methylenedioxy group of podophyllotoxin will lead to a less active compound and that the C-4 position of podophyllotoxin was the important modification location. A quantitative structure-activity relationship (QSAR) model was developed by genetic algorithm combined with multiple linear regression (GA-MLR). For this model, the squared correlation coefficient (R(2)) is 0.914, the leave-one-out cross-validation correlation coefficient (Q(2)(LOO)) is 0.881, and the root-mean-square error (RMSE) is 0.024. Five descriptors, BEHm2, Mor14v, Wap, G1v, and RDF020e, are likely to influence the biological activity of these compounds. Among them, two important ones are BEHm2 and Mor14v. This study will pave the way for further design, structural modification, and development of podophyllotoxin derivatives as insecticidal agents. PMID:23278333

  11. The use of quantitative structure-activity relationship models to develop optimized processes for the removal of tobacco host cell proteins during biopharmaceutical production.

    PubMed

    Buyel, J F; Woo, J A; Cramer, S M; Fischer, R

    2013-12-27

    The production of recombinant pharmaceutical proteins in plants benefits from the low cost of upstream production and the greater scalability of plants compared to fermenter-based systems. Now that manufacturing processes that comply with current good manufacturing practices have been developed, plants can compete with established platforms on equal terms. However, the costs of downstream processing remain high, in part because of the dedicated process steps required to remove plant-specific process-related impurities. We therefore investigated whether the ideal strategy for the chromatographic removal of tobacco host cell proteins can be predicted by quantitative structure-activity relationship (QSAR) modeling to reduce the process development time and overall costs. We identified more than 100 tobacco proteins by mass spectrometry and their structures were reconstructed from X-ray crystallography, nuclear magnetic resonance spectroscopy and/or homology modeling data. The resulting three-dimensional models were used to calculate protein descriptors, and significant descriptors were selected based on recently-published retention data for model proteins to develop QSAR models for protein retention on anion, cation and mixed-mode resins. The predicted protein retention profiles were compared with experimental results using crude tobacco protein extracts. Because of the generic nature of the method, it can easily be transferred to other expression systems such as mammalian cells. The quality of the models and potential improvements are discussed. PMID:24268820

  12. Structural properties of fluorozirconate-based glass ceramics doped with multivalent europium

    PubMed Central

    Paßlick, C.; Müller, O.; Lützenkirchen-Hecht, D.; Frahm, R.; Johnson, J. A.; Schweizer, S.

    2011-01-01

    The structure/property relationships of fluorochlorozirconate glass ceramics as a function of divalent and trivalent europium (Eu) co-doping and thermal processing have been investigated; the influence of doping ratio on the formation of barium chloride (BaCl2) nanocrystals therein was elucidated. X-ray absorption near-edge structure spectroscopy shows that the post-thermal annealing changes the Eu valence of the as-poured glass slightly, but during the melting process Eu3+ is more strongly reduced to Eu2+, in particular, when doped as a chloride instead of fluoride compound. The Eu2+-to-Eu3+ doping ratio also plays a significant role in chemical equilibrium in the melt. X-ray diffraction measurements indicate that a higher Eu2+ fraction leads to a BaCl2 phase transition from hexagonal to orthorhombic structure at a lower temperature. PMID:22275772

  13. Electronic and structural properties of ultrathin tungsten nanowires and nanotubes by density functional theory calculation

    SciTech Connect

    Sun, Shih-Jye; Lin, Ken-Huang; Li, Jia-Yun; Ju, Shin-Pon

    2014-10-07

    The simulated annealing basin-hopping method incorporating the penalty function was used to predict the lowest-energy structures for ultrathin tungsten nanowires and nanotubes of different sizes. These predicted structures indicate that tungsten one-dimensional structures at this small scale do not possess B.C.C. configuration as in bulk tungsten material. In order to analyze the relationship between multi-shell geometries and electronic transfer, the electronic and structural properties of tungsten wires and tubes including partial density of state and band structures which were determined and analyzed by quantum chemistry calculations. In addition, in order to understand the application feasibility of these nanowires and tubes on nano-devices such as field emitters or chemical catalysts, the electronic stability of these ultrathin tungsten nanowires was also investigated by density functional theory calculations.

  14. Structural properties of fluorozirconate-based glass ceramics doped with multivalent europium

    SciTech Connect

    Passlick, C.; Mueller, O.; Luetzenkirchen-Hecht, D.; Frahm, R.; Johnson, J. A.; Schweizer, S.

    2011-12-01

    The structure/property relationships of fluorochlorozirconate glass ceramics as a function of divalent and trivalent europium (Eu) co-doping and thermal processing have been investigated; the influence of doping ratio on the formation of barium chloride (BaCl{sub 2}) nanocrystals therein was elucidated. X-ray absorption near-edge structure spectroscopy shows that the post-thermal annealing changes the Eu valence of the as-poured glass slightly, but during the melting process Eu{sup 3+} is more strongly reduced to Eu{sup 2+}, in particular, when doped as a chloride instead of fluoride compound. The Eu{sup 2+}-to-Eu{sup 3+} doping ratio also plays a significant role in chemical equilibrium in the melt. X-ray diffraction measurements indicate that a higher Eu{sup 2+} fraction leads to a BaCl{sub 2} phase transition from hexagonal to orthorhombic structure at a lower temperature.

  15. Predictions of Cleavability of Calpain Proteolysis by Quantitative Structure-Activity Relationship Analysis Using Newly Determined Cleavage Sites and Catalytic Efficiencies of an Oligopeptide Array*

    PubMed Central

    Shinkai-Ouchi, Fumiko; Koyama, Suguru; Ono, Yasuko; Hata, Shoji; Ojima, Koichi; Shindo, Mayumi; duVerle, David; Ueno, Mika; Kitamura, Fujiko; Doi, Naoko; Takigawa, Ichigaku; Mamitsuka, Hiroshi; Sorimachi, Hiroyuki

    2016-01-01

    Calpains are intracellular Ca2+-regulated cysteine proteases that are essential for various cellular functions. Mammalian conventional calpains (calpain-1 and calpain-2) modulate the structure and function of their substrates by limited proteolysis. Thus, it is critically important to determine the site(s) in proteins at which calpains cleave. However, the calpains' substrate specificity remains unclear, because the amino acid (aa) sequences around their cleavage sites are very diverse. To clarify calpains' substrate specificities, 84 20-mer oligopeptides, corresponding to P10-P10′ of reported cleavage site sequences, were proteolyzed by calpains, and the catalytic efficiencies (kcat/Km) were globally determined by LC/MS. This analysis revealed 483 cleavage site sequences, including 360 novel ones. The kcat/Kms for 119 sites ranged from 12.5–1,710 M−1s−1. Although most sites were cleaved by both calpain-1 and −2 with a similar kcat/Km, sequence comparisons revealed distinct aa preferences at P9-P7/P2/P5′. The aa compositions of the novel sites were not statistically different from those of previously reported sites as a whole, suggesting calpains have a strict implicit rule for sequence specificity, and that the limited proteolysis of intact substrates is because of substrates' higher-order structures. Cleavage position frequencies indicated that longer sequences N-terminal to the cleavage site (P-sites) were preferred for proteolysis over C-terminal (P′-sites). Quantitative structure-activity relationship (QSAR) analyses using partial least-squares regression and >1,300 aa descriptors achieved kcat/Km prediction with r = 0.834, and binary-QSAR modeling attained an 87.5% positive prediction value for 132 reported calpain cleavage sites independent of our model construction. These results outperformed previous calpain cleavage predictors, and revealed the importance of the P2, P3′, and P4′ sites, and P1-P2 cooperativity. Furthermore, using our

  16. Predictions of Cleavability of Calpain Proteolysis by Quantitative Structure-Activity Relationship Analysis Using Newly Determined Cleavage Sites and Catalytic Efficiencies of an Oligopeptide Array.

    PubMed

    Shinkai-Ouchi, Fumiko; Koyama, Suguru; Ono, Yasuko; Hata, Shoji; Ojima, Koichi; Shindo, Mayumi; duVerle, David; Ueno, Mika; Kitamura, Fujiko; Doi, Naoko; Takigawa, Ichigaku; Mamitsuka, Hiroshi; Sorimachi, Hiroyuki

    2016-04-01

    Calpains are intracellular Ca(2+)-regulated cysteine proteases that are essential for various cellular functions. Mammalian conventional calpains (calpain-1 and calpain-2) modulate the structure and function of their substrates by limited proteolysis. Thus, it is critically important to determine the site(s) in proteins at which calpains cleave. However, the calpains' substrate specificity remains unclear, because the amino acid (aa) sequences around their cleavage sites are very diverse. To clarify calpains' substrate specificities, 84 20-mer oligopeptides, corresponding to P10-P10' of reported cleavage site sequences, were proteolyzed by calpains, and the catalytic efficiencies (kcat/Km) were globally determined by LC/MS. This analysis revealed 483 cleavage site sequences, including 360 novel ones. Thekcat/Kms for 119 sites ranged from 12.5-1,710 M(-1)s(-1) Although most sites were cleaved by both calpain-1 and -2 with a similarkcat/Km, sequence comparisons revealed distinct aa preferences at P9-P7/P2/P5'. The aa compositions of the novel sites were not statistically different from those of previously reported sites as a whole, suggesting calpains have a strict implicit rule for sequence specificity, and that the limited proteolysis of intact substrates is because of substrates' higher-order structures. Cleavage position frequencies indicated that longer sequences N-terminal to the cleavage site (P-sites) were preferred for proteolysis over C-terminal (P'-sites). Quantitative structure-activity relationship (QSAR) analyses using partial least-squares regression and >1,300 aa descriptors achievedkcat/Kmprediction withr= 0.834, and binary-QSAR modeling attained an 87.5% positive prediction value for 132 reported calpain cleavage sites independent of our model construction. These results outperformed previous calpain cleavage predictors, and revealed the importance of the P2, P3', and P4' sites, and P1-P2 cooperativity. Furthermore, using our binary-QSAR model

  17. A chrysophyte-based quantitative reconstruction of winter severity from varved lake sediments in NE Poland during the past millennium and its relationship to natural climate variability

    NASA Astrophysics Data System (ADS)

    Hernández-Almeida, I.; Grosjean, M.; Przybylak, R.; Tylmann, W.

    2015-08-01

    Chrysophyte cysts are recognized as powerful proxies of cold-season temperatures. In this paper we use the relationship between chrysophyte assemblages and the number of days below 4 °C (DB4 °C) in the epilimnion of a lake in northern Poland to develop a transfer function and to reconstruct winter severity in Poland for the last millennium. DB4 °C is a climate variable related to the length of the winter. Multivariate ordination techniques were used to study the distribution of chrysophytes from sediment traps of 37 low-land lakes distributed along a variety of environmental and climatic gradients in northern Poland. Of all the environmental variables measured, stepwise variable selection and individual Redundancy analyses (RDA) identified DB4 °C as the most important variable for chrysophytes, explaining a portion of variance independent of variables related to water chemistry (conductivity, chlorides, K, sulfates), which were also important. A quantitative transfer function was created to estimate DB4 °C from sedimentary assemblages using partial least square regression (PLS). The two-component model (PLS-2) had a coefficient of determination of Rcross2  = 0.58, with root mean squared error of prediction (RMSEP, based on leave-one-out) of 3.41 days. The resulting transfer function was applied to an annually-varved sediment core from Lake Żabińskie, providing a new sub-decadal quantitative reconstruction of DB4 °C with high chronological accuracy for the period AD 1000-2010. During Medieval Times (AD 1180-1440) winters were generally shorter (warmer) except for a decade with very long and severe winters around AD 1260-1270 (following the AD 1258 volcanic eruption). The 16th and 17th centuries and the beginning of the 19th century experienced very long severe winters. Comparison with other European cold-season reconstructions and atmospheric indices for this region indicates that large parts of the winter variability (reconstructed DB4 °C) is due

  18. TECHNIQUES FOR THE STUDY OF THE STRUCTURAL PROPERTIES.

    SciTech Connect

    FERNANDEZ-GARCIA, M.; RODRIGUEZ, J.A.; MARTINEZ-ARIAS, A.; HANSON, J.C.

    2006-06-30

    The evolution of our understanding of the behavior of oxide nanostructures depends heavily on the structural information obtained from a wide range of physical methods traditionally used in solid state physics, surface science and inorganic chemistry. In this chapter, we describe several techniques that are useful for the characterization of the structural properties of oxide nanostructures: X-ray diffraction (XRD) and scattering, X-ray absorption fine structure (XAFS), Raman spectroscopy, transmission electron microscopy (TEM), scanning tunneling microscopy (STM) and atomic force microscopy (AFM). The ultimate goal is to obtain information about the spatial arrangement of atoms in the nanostructures with precise interatomic distances and bond angles. This may not be possible for complex systems and one may get only partial information about the local geometry or morphology.

  19. Electronic, Thermal and Structural Properties of Graphene Oxide Frameworks

    SciTech Connect

    Zhu, Pan; Sumpter, Bobby G; Meunier, V.

    2013-01-01

    We report a theoretical study of the electronic, thermal, and structural properties of a series of graphene oxide frameworks (GOFs) using first-principles calculations based on density functional theory. The molecular structure of GOFs is systematically studied by varying the nature and concentration of linear boronic acid pillars and the thermal stability is assessed using ab initio molecular dynamics. The results demonstrate that GOFs are thermally stable up to 550 K and that electronic properties, such as their band gap, can be modified controllably by an appropriate choice of pillaring unit and pillar concentration. The tunability of the electronic structure using non-chemical means, e.g., mechanical strain, is also quantified. Overall, this class of materials is predicted to offer highly tunable materials electronic properties ranging from metallic to semiconducting.

  20. Electronic, Thermal, and Structural Properties of Graphene Oxide Frameworks

    SciTech Connect

    Zhu, Pan; Sumpter, Bobby G; Meunier, V.

    2013-01-01

    We report a theoretical study of the electronic, thermal, and structural properties of a series of graphene oxide frameworks (GOFs) using first-principles calculations based on density functional theory. The molecular structure of GOFs is systematically studied by varying the nature and concentration of linear boronic acid pillars, and the thermal stability is assessed using ab initio molecular dynamics. The results demonstrate that GOFs are thermally stable up to 550 K and that electronic properties, such as their band gap, can be modified controllably by an appropriate choice of pillaring unit and pillar concentration. The tunability of the electronic structure using nonchemical means, e.g., mechanical strain, is also quantified. Overall, this class of materials is predicted to offer highly tunable materials electronic properties ranging from metallic to semiconducting.

  1. Studies on structural properties of clay magnesium ferrite nano composite

    NASA Astrophysics Data System (ADS)

    Kaur, Manpreet; Singh, Mandeep; Jeet, Kiran; Kaur, Rajdeep

    2015-08-01

    Magnesium ferrite-bentonite clay composite was prepared by sol-gel combustion method employing citric acid as complexing agent and fuel. The effect of clay on the structural properties was studied with X-ray diffraction (XRD), Fourier transform infrared (FT-IR) Spectroscopy, Scanning electron microscopy (SEM), SEM- Energy dispersive Spectroscope (EDS) and BET surface area analyzer. Decrease in particle size and density was observed on addition of bentonite clay. The BET surface area of nano composite containing just 5 percent clay was 74.86 m2/g. Whereas porosity increased from 40.5 per cent for the pure magnesium ferrite to 81.0 percent in the composite showing that nano-composite has potential application as an adsorbent.

  2. Structural properties of bismuth-bearing semiconductor alloys

    NASA Technical Reports Server (NTRS)

    Berding, M. A.; Sher, A.; Chen, A.-B.; Miller, W. E.

    1988-01-01

    The structural properties of bismuth-bearing III-V semiconductor alloys InPBi, InAsBi, and InSbBi were studied theoretically. Bond energies, bond lengths, and strain coefficients were calculated for pure AlBi, GaBi, and InBi compounds and their alloys, and predictions were made for the mixing enthalpies, miscibility gaps, and critical metastable-to-stable material transition temperatures. Miscibility calculations indicate that InSbBi will be the most miscible, and the InPBi will be the the most difficult to mix. However, calculations of the hardness of the Bi compounds indicate that, once formed, the InPBi alloy will be harder than the other Bi alloys and substantially harder than the currently favored narrow-gap semiconductor HgCdTe.

  3. Studies on structural properties of clay magnesium ferrite nano composite

    SciTech Connect

    Kaur, Manpreet Singh, Mandeep; Jeet, Kiran Kaur, Rajdeep

    2015-08-28

    Magnesium ferrite-bentonite clay composite was prepared by sol-gel combustion method employing citric acid as complexing agent and fuel. The effect of clay on the structural properties was studied with X-ray diffraction (XRD), Fourier transform infrared (FT-IR) Spectroscopy, Scanning electron microscopy (SEM), SEM- Energy dispersive Spectroscope (EDS) and BET surface area analyzer. Decrease in particle size and density was observed on addition of bentonite clay. The BET surface area of nano composite containing just 5 percent clay was 74.86 m{sup 2}/g. Whereas porosity increased from 40.5 per cent for the pure magnesium ferrite to 81.0 percent in the composite showing that nano-composite has potential application as an adsorbent.

  4. Electronic and Structural Properties of Transition - and Transition-Metal Surfaces

    NASA Astrophysics Data System (ADS)

    Chan, Che-Ting

    The electronic and structural properties of transition metals and transition metal surfaces are studied theoretically from first-principles, with emphasis on understanding their properties under different physical and chemical environments. A new general self-consistency procedure for calculating the electronic structure of crystalline solids is developed and applied to extend a first-principles pseudopotential linear combination of atomic orbitals (LCAO) method to full point-by-point self-consistency. This scheme is tested by applying to a study of the structural and electronic properties of Si and W, prototypical systems of very different bonding characters. The importance of self-consistency is investigated. The structural properties of Mo and W in the bcc, fcc and hcp structures are calculated with the new scheme. Equilibrium lattice constants, cohesive energies, bulk moduli, differences in structural energies and Mulliken population analyses are obtained. For both elements, the cohesive energies decrease in the order E(,coh)('bcc) > E(,coh)('fcc) (DBLTURN) E(,coh)('hcp). The results show that the relative stability of the bcc and fcc structures can be explained qualitatively but not quantitatively by the difference in the sum of the electronic eigenvalues. The structural properties of the W(001)(1 x 1) surface are also calculated with the same method. Surface energy, top layer relaxation, and relaxation energy are obtained with good agreement with available experimental data. The electronic structures of PdH and Pd(,4)H are calculated by a pseudopotential mixed basis approach with emphasis on the nature of the Pd-H bonding state and the effect of changing hydrogen concentration. The essential physical nature of the hydride system is summarized in a simple conceptual model. The mixed basis method is then applied to study the electronic structures of monolayer atomic hydrogen at surface and subsurface sites of the Pd(111) surface. Electronic properties and

  5. Support vector regression-guided unravelling: antioxidant capacity and quantitative structure-activity relationship predict reduction and promotion effects of flavonoids on acrylamide formation.

    PubMed

    Huang, Mengmeng; Wei, Yan; Wang, Jun; Zhang, Yu

    2016-01-01

    We used the support vector regression (SVR) approach to predict and unravel reduction/promotion effect of characteristic flavonoids on the acrylamide formation under a low-moisture Maillard reaction system. Results demonstrated the reduction/promotion effects by flavonoids at addition levels of 1-10000 μmol/L. The maximal inhibition rates (51.7%, 68.8% and 26.1%) and promote rates (57.7%, 178.8% and 27.5%) caused by flavones, flavonols and isoflavones were observed at addition levels of 100 μmol/L and 10000 μmol/L, respectively. The reduction/promotion effects were closely related to the change of trolox equivalent antioxidant capacity (ΔTEAC) and well predicted by triple ΔTEAC measurements via SVR models (R: 0.633-0.900). Flavonols exhibit stronger effects on the acrylamide formation than flavones and isoflavones as well as their O-glycosides derivatives, which may be attributed to the number and position of phenolic and 3-enolic hydroxyls. The reduction/promotion effects were well predicted by using optimized quantitative structure-activity relationship (QSAR) descriptors and SVR models (R: 0.926-0.994). Compared to artificial neural network and multi-linear regression models, SVR models exhibited better fitting performance for both TEAC-dependent and QSAR descriptor-dependent predicting work. These observations demonstrated that the SVR models are competent for predicting our understanding on the future use of natural antioxidants for decreasing the acrylamide formation. PMID:27586851

  6. Mechanistic quantitative structure-activity relationship model for the photoinduced toxicity of polycyclic aromatic hydrocarbons. 1: Physical model based on chemical kinetics in a two-compartment system

    SciTech Connect

    Krylov, S.N.; Huang, X.D.; Zeiler, L.F.; Dixon, D.G.; Greenberg, B.M.

    1997-11-01

    A quantitative structure-activity relationship model for the photoinduced toxicity of 16 polycyclic aromatic hydrocarbons (PAHs) to duckweed (Lemna gibba) in simulated solar radiation (SSR) was developed. Lemna gibba was chosen for this study because toxicity could be considered in two compartments: water column and leaf tissue. Modeling of photoinduced toxicity was described by photochemical reactions between PAHs and a hypothetical group of endogenous biomolecules (G) required for normal growth, with damage to G by PAHs and/or photomodified PAHs in SSR resulting in impaired growth. The reaction scheme includes photomodification of PAHs, uptake of PAHs into leaves, triplet-state formation of intact PAHs, photosensitization reactions that damage G, and reactions between photomodified PAHs and G. The assumptions used were: the PAH photomodification rate is slower than uptake of chemicals into leaves, the PAH concentration in aqueous solution is nearly constant during a toxicity test, the fluence rate of actinic radiation is lower within leaves than in the aqueous phase, and the toxicity of intact PAHs in the dark is negligible. A series of differential equations describing the reaction kinetics of intact and photomodifed PAHs with G was derived. The resulting equation for PAH toxicity was a function of treatment period, initial PAH concentration, relative absorbance of SSR by each PAH, quantum yield for formation of triplet-state PAH, and rate of PAH photomodification. Data for growth in the presence of intact and photomodified PAHs were used to empirically solve for a photosensitization constant (PSC) and a photomodification constant (PMC) for each of the 16 PAHs tested. For 9 PAHs the PMC dominates and for 7 PAHs the PSC dominates.

  7. Toxicity of aryl- and benzylhalides to Daphnia magna and classification of their mode of action based on quantitative structure-activity relationship

    SciTech Connect

    Marchini, S.; Passerini, L.; Hoglund, M.D.; Pino, A.; Nendza, M.

    1999-12-01

    The acute toxicity of aryl- and benzylhalides to Daphnia magna was investigated to test the validity of existing classification schemes for chemicals by mode of action, mainly based on fish studies, and the applicability of predictive quantitative structure-activity relationship (QSAR) models. Halobenzenes and halotoluenes are generally agreed to be unambiguous baseline toxicants (class 1) with the major exception of the benzylic structures, which are reactive in fish tests (class 3). Eighty-nine percent of the arylhalides tested in this study match a log P{sub ow}-dependent QSAR, including fluorinated, chlorinated, brominated, and iodinated derivatives, thereby confirming the validity of the baseline models also for variously halogenated compounds (other than only-chloro compounds). The toxicities of the benzylhalides relative to baseline QSARs clearly indicate that these compounds belong to two classes of mode of action, i.e., they either act as narcotic toxicants (class 1) or reveal excess toxicity due to unspecific reactivity (class 3). On some occasions, the assignment to the two classes of F. magna deviates from the structural rules derived from fish, i.e., iodinated compounds as well as {alpha},{alpha}-Cl{sub 2}-toluene's lack reactive excess toxicity but behave as nonpolar nonspecific toxicants. The QSARs derived during this study reveal lower slopes and higher intercepts than typical baseline models and, together with the analysis of mixture toxicity studies, behavioral studies, and critical body burden, advocate the hypothesis that there are several different ways to produce baseline toxicity. Most halobenzenes and halotoluenes are actually baseline chemicals with some extra reactivity and as such form a subgroup, whose limits still have to be defined. Different primary sites of action could explain why the chemicals are discriminated by different classification systems, but still they must have some rate-limiting interaction in common as they fit the

  8. Support vector regression-guided unravelling: antioxidant capacity and quantitative structure-activity relationship predict reduction and promotion effects of flavonoids on acrylamide formation

    PubMed Central

    Huang, Mengmeng; Wei, Yan; Wang, Jun; Zhang, Yu

    2016-01-01

    We used the support vector regression (SVR) approach to predict and unravel reduction/promotion effect of characteristic flavonoids on the acrylamide formation under a low-moisture Maillard reaction system. Results demonstrated the reduction/promotion effects by flavonoids at addition levels of 1–10000 μmol/L. The maximal inhibition rates (51.7%, 68.8% and 26.1%) and promote rates (57.7%, 178.8% and 27.5%) caused by flavones, flavonols and isoflavones were observed at addition levels of 100 μmol/L and 10000 μmol/L, respectively. The reduction/promotion effects were closely related to the change of trolox equivalent antioxidant capacity (ΔTEAC) and well predicted by triple ΔTEAC measurements via SVR models (R: 0.633–0.900). Flavonols exhibit stronger effects on the acrylamide formation than flavones and isoflavones as well as their O-glycosides derivatives, which may be attributed to the number and position of phenolic and 3-enolic hydroxyls. The reduction/promotion effects were well predicted by using optimized quantitative structure-activity relationship (QSAR) descriptors and SVR models (R: 0.926–0.994). Compared to artificial neural network and multi-linear regression models, SVR models exhibited better fitting performance for both TEAC-dependent and QSAR descriptor-dependent predicting work. These observations demonstrated that the SVR models are competent for predicting our understanding on the future use of natural antioxidants for decreasing the acrylamide formation. PMID:27586851

  9. Relationship between self-reported high-heeled shoe use and bone mineral density using quantitative ultrasound at a community health fair.

    PubMed

    Glassy, Crystal M; Glassy, Matthew S; Guggenheim, Carla

    2013-01-01

    This is the first known study to examine the relationship between high-heel use and bone mineral density (BMD). Because women are disproportionately affected by osteoporosis, it is important to identify possible modifiable behaviors of women that may adversely affect bone health. Many studies have shown changes in body mechanics when wearing high-heeled shoes in comparison to normal gait. Because the composition of bone changes according to mechanical load and muscle activity, this study investigates whether wearing high heels may alter BMD. Two hundred and twenty-one participants at a community health fair in Lansing, Michigan, were surveyed on high-heel use and bone health risk (gender, thin/small frame, fair skin, family history of fracture, smoking history, walking, dairy consumption, and early menopause or oopherectomy at <45 years old). Quantitative ultrasound (QUS) of the heel by Hologic's Sahara Sonometer was used to measure BMD. The mean age was 45.2 (SD 13.7) years, and the majority of participants were female (208, 94 %). A significant difference between mean BMD and high-heel use was not found. Independent correlations existed between fair skinned/sunburn easily and BMD, r(212) = -0.14, p = 0.038, as well as history of smoking and BMD, r(212) = -0.14, p = 0.042. Bone health risk score was strongly correlated with heel use binary variable "yes/no," r(210) = 0.21, p = 0.003. Our study suggests that wearing high-heeled shoes does not lead to appreciable differences in BMD among community health fair participants as assessed by QUS. PMID:22983265

  10. Interspecies quantitative structure-toxicity-toxicity (QSTTR) relationship modeling of ionic liquids. Toxicity of ionic liquids to V. fischeri, D. magna and S. vacuolatus.

    PubMed

    Das, Rudra Narayan; Roy, Kunal; Popelier, Paul L A

    2015-12-01

    Considering the increasing uses of ionic liquids (ILs) in various industrial processes and chemical engineering operations, a complete assessment of their hazardous profile is essential. In the absence of adequate experimental data, in silico modeling might be helpful in filling data gaps for the toxicity of ILs towards various ecological indicator organisms. Using the rationale of taxonomic relatedness, the development of predictive quantitative structure-toxicity-toxicity relationship (QSTTR) models allows predicting the toxicity of ILs to a particular species using available experimental toxicity data towards a different species. Such studies may employ, along with the available experimental toxicity data to a species, molecular structure features and physicochemical properties of chemicals as independent variables for prediction of the toxicity profile against another closely related species. A few such interspecies toxicity correlation models have been reported in the literature for diverse chemicals in general, but this approach has been rarely applied to the class of ionic liquids. The present study involves the use of IL toxicity data towards the bacteria Vibrio fischeri along with molecular structure derived information or computational descriptors like extended topochemical atom (ETA) indices, quantum topological molecular similarity (QTMS) descriptors and computed lipophilicity measure (logk0) for the interspecies exploration of the toxicity data towards green algae S. vacuolatus and crustacea Daphnia magna, separately. This modeling study has been performed in accordance with the OECD guidelines. Finally, predictions for a true external set have been performed to fill the data gap of toxicity towards daphnids and algae using the Vibrio toxicity data and molecular structure attributes. PMID:26414597

  11. Establishing the Quantitative Relationship Between Lanreotide Autogel®, Chromogranin A, and Progression-Free Survival in Patients with Nonfunctioning Gastroenteropancreatic Neuroendocrine Tumors.

    PubMed

    Buil-Bruna, Núria; Dehez, Marion; Manon, Amandine; Nguyen, Thi Xuan Quyen; Trocóniz, Iñaki F

    2016-05-01

    The objective of this work was to establish the quantitative relationship between Lanreotide Autogel® (LAN) on serum chromogranin A (CgA) and progression-free survival (PFS) in patients with nonfunctioning gastroenteropancreatic neuroendocrine tumors (GEP-NETs) through an integrated pharmacokinetic/pharmacodynamic (PK/PD) model. In CLARINET, a phase III, randomized, double-blind, placebo-controlled study, 204 patients received deep subcutaneous injections of LAN 120 mg (n = 101) or placebo (n = 103) every 4 weeks for 96 weeks. Data for 810 LAN and 1298 CgA serum samples (n = 632 placebo and n = 666 LAN) were used to develop a parametric time-to-event model to relate CgA levels and PFS (76 patients experienced disease progression: n = 49 placebo and n = 27 LAN). LAN serum profiles were described by a one-compartment disposition model. Absorption was characterized by two parallel pathways following first- and zero-order kinetics. As PFS data were considered informative dropouts, CgA and PFS responses were modeled jointly. The LAN-induced decrease in CgA levels was described by an inhibitory E MAX model. Patient age and target lesions at baseline were associated with an increment in baseline CgA. Weibull model distribution showed that decreases in CgA from baseline reduced the hazard of disease progression significantly (P < 0.001). Covariates of tumor location in the pancreas and tumor hepatic tumor load were associated with worse prognosis (P < 0.001). We established a semimechanistic PK/PD model to better understand the effect of LAN on a surrogate endpoint (serum CgA) and ultimately the clinical endpoint (PFS) in treatment-naive patients with nonfunctioning GEP-NETs. PMID:26908127

  12. Synthesis and quantitative structure-activity relationship (QSAR) study of novel N-arylsulfonyl-3-acylindole arylcarbonyl hydrazone derivatives as nematicidal agents.

    PubMed

    Che, Zhiping; Zhang, Shaoyong; Shao, Yonghua; Fan, Lingling; Xu, Hui; Yu, Xiang; Zhi, Xiaoyan; Yao, Xiaojun; Zhang, Rui

    2013-06-19

    In continuation of our program aimed at the discovery and development of natural-product-based pesticidal agents, 54 novel N-arylsulfonyl-3-acylindole arylcarbonyl hydrazone derivatives were prepared, and their structures were well characterized by ¹H NMR, ¹³C NMR, HRMS, ESI-MS, and mp. Their nematicidal activity was evaluated against that of the pine wood nematode, Bursaphelenchus xylophilus in vivo. Among all of the derivatives, especially V-12 and V-39 displayed the best promising nematicidal activity with LC₅₀ values of 1.0969 and 1.2632 mg/L, respectively. This suggested that introduction of R¹ and R² together as the electron-withdrawing substituents, R³ as the methyl group, and R⁴ as the phenyl with the electron-donating substituents could be taken into account for further preparation of these kinds of compounds as nematicidal agents. Six selected descriptors are a WHIM descriptor (E1m), two GETAWAY descriptors (R1m+ and R3m+), a Burden eigenvalues descriptor (BEHm8), and two edge-adjacency index descriptors (EEig05x and EEig13d). Quantitative structure-activity relationship (QSAR) studies demonstrated that the structural factors, such as molecular mass (a negative correlation with the bioactivity) and molecular polarity (a positive correlation with bioactivity), are likely to govern the nematicidal activities of these compounds. For this model, the correlation coefficient (R²(training set)), the leave-one-out cross-validation correlation coefficient (Q²(LOO)), and the 7-fold cross-validation correlation coefficient (Q²(7-fold)) were 0.791, 0.701, and 0.715, respectively. The external cross-validation correlation coefficient (Q²ext) and the root-mean-square error for the test set (RMSE(test set)) were 0.774 and 3.412, respectively. This study will pave the way for future design, structural modification, and development of indole derivatives as nematicidal agents. PMID:23738496

  13. Structure-based approach to pharmacophore identification, in silico screening, and three-dimensional quantitative structure-activity relationship studies for inhibitors of Trypanosoma cruzi dihydrofolate reductase function

    SciTech Connect

    Schormann, N.; Senkovich, O.; Walker, K.; Wright, D.L.; Anderson, A.C.; Rosowsky, A.; Ananthan, S.; Shinkre, B.; Velu, S.; Chattopadhyay, D.

    2009-07-10

    We have employed a structure-based three-dimensional quantitative structure-activity relationship (3D-QSAR) approach to predict the biochemical activity for inhibitors of T. cruzi dihydrofolate reductase-thymidylate synthase (DHFR-TS). Crystal structures of complexes of the enzyme with eight different inhibitors of the DHFR activity together with the structure in the substrate-free state (DHFR domain) were used to validate and refine docking poses of ligands that constitute likely active conformations. Structural information from these complexes formed the basis for the structure-based alignment used as input for the QSAR study. Contrary to indirect ligand-based approaches the strategy described here employs a direct receptor-based approach. The goal is to generate a library of selective lead inhibitors for further development as antiparasitic agents. 3D-QSAR models were obtained for T. cruzi DHFR-TS (30 inhibitors in learning set) and human DHFR (36 inhibitors in learning set) that show a very good agreement between experimental and predicted enzyme inhibition data. For crossvalidation of the QSAR model(s), we have used the 10% leave-one-out method. The derived 3D-QSAR models were tested against a few selected compounds (a small test set of six inhibitors for each enzyme) with known activity, which were not part of the learning set, and the quality of prediction of the initial 3D-QSAR models demonstrated that such studies are feasible. Further refinement of the models through integration of additional activity data and optimization of reliable docking poses is expected to lead to an improved predictive ability.

  14. Prediction of blood-brain barrier permeation of α-adrenergic and imidazoline receptor ligands using PAMPA technique and quantitative-structure permeability relationship analysis.

    PubMed

    Vucicevic, Jelica; Nikolic, Katarina; Dobričić, Vladimir; Agbaba, Danica

    2015-02-20

    Imidazoline receptor ligands are a numerous family of biologically active compounds known to produce central hypotensive effect by interaction with both α2-adrenoreceptors (α2-AR) and imidazoline receptors (IRs). Recent hypotheses connect those ligands with several neurological disorders. Therefore some IRs ligands are examined as novel centrally acting antihypertensives and drug candidates for treatment of various neurological diseases. Effective Blood-Brain Barrier (BBB) permeability (P(e)) of 18 IRs/α-ARs ligands and 22 Central Nervous System (CNS) drugs was experimentally determined using Parallel Artificial Membrane Permeability Assay (PAMPA) and studied by the Quantitative-Structure-Permeability Relationship (QSPR) methodology. The dominant molecules/cations species of compounds have been calculated at pH = 7.4. The analyzed ligands were optimized using Density Functional Theory (B3LYP/6-31G(d,p)) included in ChemBio3D Ultra 13.0 program and molecule descriptors for optimized compounds were calculated using ChemBio3D Ultra 13.0, Dragon 6.0 and ADMET predictor 6.5 software. Effective permeability of compounds was used as dependent variable (Y), while calculated molecular parametres were used as independent variables (X) in the QSPR study. SIMCA P+ 12.0 was used for Partial Least Square (PLS) analysis, while the stepwise Multiple Linear Regression (MLR) and Artificial Neural Networks (ANN) modeling were performed using STASTICA Neural Networks 4.0. Predictive potential of the formed models was confirmed by Leave-One-Out Cross- and external-validation and the most reliable models were selected. The descriptors that are important for model building are identified as well as their influence on BBB permeability. Results of the QSPR studies could be used as time and cost efficient screening tools for evaluation of BBB permeation of novel α-adrenergic/imidazoline receptor ligands, as promising drug candidates for treatment of hypertension or neurological diseases

  15. Investigating the Quantitative Structure-Activity Relationships for Antibody Recognition of Two Immunoassays for Polycyclic Aromatic Hydrocarbons by Multiple Regression Methods

    PubMed Central

    Zhang, Yan-Feng; Zhang, Li; Gao, Zhi-Xian; Dai, Shu-Gui

    2012-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous contaminants found in the environment. Immunoassays represent useful analytical methods to complement traditional analytical procedures for PAHs. Cross-reactivity (CR) is a very useful character to evaluate the extent of cross-reaction of a cross-reactant in immunoreactions and immunoassays. The quantitative relationships between the molecular properties and the CR of PAHs were established by stepwise multiple linear regression, principal component regression and partial least square regression, using the data of two commercial enzyme-linked immunosorbent assay (ELISA) kits. The objective is to find the most important molecular properties that affect the CR, and predict the CR by multiple regression methods. The results show that the physicochemical, electronic and topological properties of the PAH molecules have an integrated effect on the CR properties for the two ELISAs, among which molar solubility (Sm) and valence molecular connectivity index (3χv) are the most important factors. The obtained regression equations for RisC kit are all statistically significant (p < 0.005) and show satisfactory ability for predicting CR values, while equations for RaPID kit are all not significant (p > 0.05) and not suitable for predicting. It is probably because that the RisC immunoassay employs a monoclonal antibody, while the RaPID kit is based on polyclonal antibody. Considering the important effect of solubility on the CR values, cross-reaction potential (CRP) is calculated and used as a complement of CR for evaluation of cross-reactions in immunoassays. Only the compounds with both high CR and high CRP can cause intense cross-reactions in immunoassays. PMID:23012547

  16. The Relationship between Student's Quantitative Skills, Application of Math, Science Courses, and Science Marks at Single-Sex Independent High Schools

    ERIC Educational Resources Information Center

    Cambridge, David

    2012-01-01

    For independent secondary schools who offer rigorous curriculum to attract students, integration of quantitative skills in the science courses has become an important definition of rigor. However, there is little research examining students' quantitative skills in relation to high school science performance within the single-sex independent…

  17. Structure-Property Correlations in Microwave Joining of Inconel 718

    NASA Astrophysics Data System (ADS)

    Bansal, Amit; Sharma, Apurbba Kumar; Kumar, Pradeep; Das, Shantanu

    2015-09-01

    The butt joining of Inconel 718 plates at 981°C solution treated and aged (981STA) condition was carried out using the microwave hybrid heating technique with Inconel 718 powder as a filler material. The developed joints were free from any microfissures (cracks) and were metallurgically bonded through complete melting of the powder particles. The as-welded joints were subjected to postweld heat treatments, including direct-aged, 981STA and 1080STA. The microstructural features of the welded joints were investigated using a field emission-scanning electron microscope equipped with x-ray elemental analysis. Microhardness and room-temperature tensile properties of the welded joints were evaluated. The postweld heat-treated specimens exhibited higher microhardness and tensile strength than the as-welded specimens due to the formation of strengthening precipitates in the microstructure after postweld heat treatments. The microhardness of the fusion zone of the joint in 1080STA condition was higher than all welded conditions due to the complete dissolution of Laves phase after 1080STA treatment. However, the tensile strength of the welded specimen in 981STA condition was higher than all welded conditions. The tensile strength in 1080STA condition was lower than that in 981STA condition because of the grain coarsening that took place after 1080STA condition. The fractography of the fractured surfaces was carried out to determine the structure-property-fracture correlation.

  18. Nanostructured ferroelectrics: fabrication and structure-property relations.

    PubMed

    Han, Hee; Kim, Yunseok; Alexe, Marin; Hesse, Dietrich; Lee, Woo

    2011-10-25

    With the continued demand for ultrahigh density ferroelectric data storage applications, it is becoming increasingly important to scale the dimension of ferroelectrics down to the nanometer-scale region and to thoroughly understand the effects of miniaturization on the materials properties. Upon reduction of the physical dimension of the material, the change in physical properties associated with size reduction becomes extremely difficult to characterize and to understand because of a complicated interplay between structures, surface properties, strain effects from substrates, domain nucleation, and wall motions. In this Review, the recent progress in fabrication and structure-property relations of nanostructured ferroelectric oxides is summarized. Various fabrication approaches are reviewed, with special emphasis on a newly developed stencil-based method for fabricating ferroelectric nanocapacitors, and advantages and limitations of the processes are discussed. Stress-induced evolutions of domain structures upon reduction of the dimension of the material and their implications on the electrical properties are discussed in detail. Distinct domain nucleation, growth, and propagation behaviors in nanometer-scale ferroelectric capacitors are discussed and compared to those of micrometer-scale counterparts. The structural effect of ferroelectric nanocapacitors on the domain switching behavior and cross-talk between neighboring capacitors under external electric field is reviewed. PMID:21919083

  19. Structural properties of particle deposits at heterogeneous surfaces

    NASA Astrophysics Data System (ADS)

    Stojiljković, D.; Šćepanović, J. R.; Vrhovac, S. B.; Švrakić, N. M.

    2015-06-01

    The random sequential adsorption (RSA) approach is used to analyze adsorption of spherical particles of a fixed radius on nonuniform flat surfaces covered by rectangular cells. The configuration of the cells (heterogeneities) was produced by performing RSA simulations to a prescribed coverage fraction θ_0{(cell)} . Adsorption was assumed to occur if the particle (projected) center lies within a rectangular cell area, i.e. if sphere touches the cells. The jammed-state properties of the model were studied for different values of cell size α (comparable with the adsorbing particle size) and density θ_0{(cell)} . Numerical simulations were carried out to investigate adsorption kinetics, jamming coverage, and structure of coverings. Structural properties of the jammed-state coverings were analyzed in terms of the radial distribution function g(r) and distribution of the Delaunay ‘free’ volumes P(v). It was demonstrated that adsorption kinetics and the jamming coverage decreased significantly, at a fixed density θ_0{(cell)} , when the cell size α increased. The predictions following from our calculation suggest that the porosity (pore volumes) of deposited monolayer can be controlled by the size and shape of landing cells, and by anisotropy of the cell deposition procedure.

  20. Structural Properties of Finite MoS2 Nanowires

    NASA Astrophysics Data System (ADS)

    Clark, Shaylyn; Salgado, Andres; Fernandez-Seivane, Lucas; Lopez-Lozano, Xochitl

    2015-03-01

    Molybdenum disulfide (MoS2) has been one of the most important catalysts used in refineries worldwide for hydrodesulfurization over the past century. In the last decade, and with the advent of nanotechnology, there has been a special interest in MoS2 nanostructures due to their high potential as novel nanocatalysts. The study of the properties of these systems is of fundamental interest for the experimental design of their catalytic activity and efficiency. In this work, we have performed ab initio density-functional calculations (DFT) to investigate the structural properties of finite MoS2 nanostrutures. All the models here presented were based on newly experimentally observed morphologies in MoS2 industrial catalysts using high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) images. We simulated STEM images of the theoretical models to compare it with the experimental ones. In contrast with infinite models, the finite models prefer a rippled/twisted structure morphology over the planar or helical ones. The rippled/twisted models appear to be structurally more stable.

  1. Unusual structural properties of polymers confined in a nanocylinder

    NASA Astrophysics Data System (ADS)

    Jiang, Zhi-Bin; Peng, Meng-Jie; Li, Lin-Ling; Zhou, Dong-Shan; Wang, Rong; Xue, Gi

    2015-07-01

    Structural properties of polymers confined in nanocylinders are investigated by Monte Carlo simulation, which is successfully used to consider the conformational property of constrained polymers. The conformational properties of the polymers close to the walls exhibit different features. The density profiles of polymers are enhanced near the wall of the nanocylinder, which shows that the packing densities differ near the wall and far from the wall. The highest densities near the wall of the nanocylinder decrease with increasing radius of the nanocylinder. Furthermore, the density excess is not only near the wall of the nanocylinder, but also shifts to the center of the nanocylinder at lower temperatures. The radius of gyration and the bond length of polymers in the nanocylinder show that the polymer chains tend to extend along the axis of the nanocylinder in highly confined nanocylinder and contract at lower temperature. Our results are very helpful in understanding the packing induced physical behaviors of polymers in nanocylinders, such as glass transition, crystallization, etc. Project supported by the National Natural Science Foundation of China (Grant Nos. 21474051, 21074053, and 51133002), the National Basic Research Program of China (Grant No. 2012CB821503), and the Program for Changjiang Scholars and Innovative Research Team in University, China.

  2. Magnetic and structural properties of MnRh thin Films

    NASA Astrophysics Data System (ADS)

    Chaturvedi, Anurag; Sepehri-Amin, Hossein; Ohkubo, Tadakatsu; Hono, Kazuhiro; Suzuki, Takao

    2016-03-01

    A systematic study of magnetic and structural properties of MnRh thin films fabricated by sputter-deposition onto silica glass has been conducted. The MnRh thin films are found to be of the CsCl-type structure, and ferromagnetic at room temperature. The MnRh thin film undergoes the magnetic phase transition between antiferromagnetic and ferromagnetic states at a temperature around 175 K and 310 K during the cooling and heating process, respectively. The temperature dependence of the magnetization shows a thermal hysteresis of about 120 K. An exchange bias field of about 450 Oe at 5 K was observed with the coercivity of 900 Oe and unidirectional anisotropy constant of about 0.45 erg/cm2. The magnetic field dependence of M-T shows that the transition temperature of about 230 K remains unchanged with increasing field during the temperature variation process. A detailed STEM-EDS analysis indicates a non-uniform compositional distribution of Mn and Rh with an average composition of Mn58Rh42 at%. A high resolution STEM-HAADF analysis reveals the compositional variations within the CsCl-type MnRh grains. It is proposed that the origin of exchange bias effect is resulted from the exchange coupling between the ferromagnetic region with Mn-rich and the antiferromagnetic region with nearly the equiatomic composition.

  3. Structural properties of bismuth-bearing semiconductor alloys

    NASA Technical Reports Server (NTRS)

    Berding, M. A.; Sher, A.; Chen, A. B.

    1986-01-01

    The structural properties of bismuth-bearing III-V semiconductor alloys are addressed. Because the Bi compounds are not known to form zincblende structures, only the anion-substituted alloys InPBi, InAsBi, and InSbBi are considered candidates as narrow-gap semiconductors. Miscibility calculations indicate that InSbBi will be the most miscible, and InPBi, with the large lattice mismatch of the constituents, will be the most difficult to mix. Calculations of the hardness of the Bi compounds indicate that, once formed, the InPBi alloy will be harder than the other Bi alloys, and substantially harder than the currently favored narrow-gap semiconductor HgCdTe. Thus, although InSbBi may be an easier material to prepare, InPBi promises to be a harder material. Growth of the Bi compounds will require high effective growth temperatures, probably attainable only through the use of nonequilibrium energy-assisted epitaxial growth techniques.

  4. Dielectric and structural properties of ferroelectric betaine arsenate films

    NASA Astrophysics Data System (ADS)

    Balashova, E. V.; Krichevtsov, B. B.; Zaitseva, N. V.; Yurko, E. I.; Svinarev, F. B.

    2014-12-01

    Ferroelectric films of betaine arsenate and partially deuterated betaine arsenate have been grown by evaporation on LiNbO3, α-Al2O3, and NdGaO3 substrates with a preliminarily deposited structure of interdigitated electrodes, as well as on the Al/glass substrate. This paper presents the results of the examination of the block structure of the films in a polarizing microscope, the X-ray diffraction analysis of their crystal structure, and the investigation of the dielectric properties in a measuring field oriented both parallel and perpendicular to the plane of the film. The transition of the films to the ferroelectric state at T = T c is accompanied by anomalies of the capacitance of the structure, an increase in the dielectric loss, and the appearance of dielectric hysteresis loops. The growth of the films from a solution of betaine arsenate in a heavy water leads to an increase in the ferroelectric transition temperature from T c = 119 K in the films without deuterium to T c = 149 K, which corresponds to the degree of deuteration of approximately 60-70%. The dielectric and structural properties of the films are compared with those of the betaine arsenate single crystals and the previously studied films of betaine phosphite and glycine phosphite.

  5. Sexual Dimorphism and Population Differences in Structural Properties of Barn Swallow (Hirundo rustica) Wing and Tail Feathers

    PubMed Central

    Pap, Péter L.; Osváth, Gergely; Aparicio, José Miguel; Bărbos, Lőrinc; Matyjasiak, Piotr; Rubolini, Diego; Saino, Nicola; Vágási, Csongor I.; Vincze, Orsolya; Møller, Anders Pape

    2015-01-01

    Sexual selection and aerodynamic forces affecting structural properties of the flight feathers of birds are poorly understood. Here, we compared the structural features of the innermost primary wing feather (P1) and the sexually dimorphic outermost (Ta6) and monomorphic second outermost (Ta5) tail feathers of barn swallows (Hirundo rustica) from a Romanian population to investigate how sexual selection and resistance to aerodynamic forces affect structural differences among these feathers. Furthermore, we compared structural properties of Ta6 of barn swallows from six European populations. Finally, we determined the relationship between feather growth bars width (GBW) and the structural properties of tail feathers. The structure of P1 indicates strong resistance against aerodynamic forces, while the narrow rachis, low vane density and low bending stiffness of tail feathers suggest reduced resistance against airflow. The highly elongated Ta6 is characterized by structural modifications such as large rachis width and increased barbule density in relation to the less elongated Ta5, which can be explained by increased length and/or high aerodynamic forces acting at the leading tail edge. However, these changes in Ta6 structure do not allow for full compensation of elongation, as reflected by the reduced bending stiffness of Ta6. Ta6 elongation in males resulted in feathers with reduced resistance, as shown by the low barb density and reduced bending stiffness compared to females. The inconsistency in sexual dimorphism and in change in quality traits of Ta6 among six European populations shows that multiple factors may contribute to shaping population differences. In general, the difference in quality traits between tail feathers cannot be explained by the GBW of feathers. Our results show that the material and structural properties of wing and tail feathers of barn swallows change as a result of aerodynamic forces and sexual selection, although the result of these

  6. Sexual Dimorphism and Population Differences in Structural Properties of Barn Swallow (Hirundo rustica) Wing and Tail Feathers.

    PubMed

    Pap, Péter L; Osváth, Gergely; Aparicio, José Miguel; Bărbos, Lőrinc; Matyjasiak, Piotr; Rubolini, Diego; Saino, Nicola; Vágási, Csongor I; Vincze, Orsolya; Møller, Anders Pape

    2015-01-01

    Sexual selection and aerodynamic forces affecting structural properties of the flight feathers of birds are poorly understood. Here, we compared the structural features of the innermost primary wing feather (P1) and the sexually dimorphic outermost (Ta6) and monomorphic second outermost (Ta5) tail feathers of barn swallows (Hirundo rustica) from a Romanian population to investigate how sexual selection and resistance to aerodynamic forces affect structural differences among these feathers. Furthermore, we compared structural properties of Ta6 of barn swallows from six European populations. Finally, we determined the relationship between feather growth bars width (GBW) and the structural properties of tail feathers. The structure of P1 indicates strong resistance against aerodynamic forces, while the narrow rachis, low vane density and low bending stiffness of tail feathers suggest reduced resistance against airflow. The highly elongated Ta6 is characterized by structural modifications such as large rachis width and increased barbule density in relation to the less elongated Ta5, which can be explained by increased length and/or high aerodynamic forces acting at the leading tail edge. However, these changes in Ta6 structure do not allow for full compensation of elongation, as reflected by the reduced bending stiffness of Ta6. Ta6 elongation in males resulted in feathers with reduced resistance, as shown by the low barb density and reduced bending stiffness compared to females. The inconsistency in sexual dimorphism and in change in quality traits of Ta6 among six European populations shows that multiple factors may contribute to shaping population differences. In general, the difference in quality traits between tail feathers cannot be explained by the GBW of feathers. Our results show that the material and structural properties of wing and tail feathers of barn swallows change as a result of aerodynamic forces and sexual selection, although the result of these

  7. Binary classification of a large collection of environmental chemicals from estrogen receptor assays by quantitative structure-activity relationship and machine learning methods.

    PubMed

    Zang, Qingda; Rotroff, Daniel M; Judson, Richard S

    2013-12-23

    There are thousands of environmental chemicals subject to regulatory decisions for endocrine disrupting potential. The ToxCast and Tox21 programs have tested ∼8200 chemicals in a broad screening panel of in vitro high-throughput screening (HTS) assays for estrogen receptor (ER) agonist and antagonist activity. The present work uses this large data set to develop in silico quantitative structure-activity relationship (QSAR) models using machine learning (ML) methods and a novel approach to manage the imbalanced data distribution. Training compounds from the ToxCast project were categorized as active or inactive (binding or nonbinding) classes based on a composite ER Interaction Score derived from a collection of 13 ER in vitro assays. A total of 1537 chemicals from ToxCast were used to derive and optimize the binary classification models while 5073 additional chemicals from the Tox21 project, evaluated in 2 of the 13 in vitro assays, were used to externally validate the model performance. In order to handle the imbalanced distribution of active and inactive chemicals, we developed a cluster-selection strategy to minimize information loss and increase predictive performance and compared this strategy to three currently popular techniques: cost-sensitive learning, oversampling of the minority class, and undersampling of the majority class. QSAR classification models were built to relate the molecular structures of chemicals to their ER activities using linear discriminant analysis (LDA), classification and regression trees (CART), and support vector machines (SVM) with 51 molecular descriptors from QikProp and 4328 bits of structural fingerprints as explanatory variables. A random forest (RF) feature selection method was employed to extract the structural features most relevant to the ER activity. The best model was obtained using SVM in combination with a subset of descriptors identified from a large set via the RF algorithm, which recognized the active and

  8. Prediction of formulation effects on dermal absorption of topically applied ectoparasiticides dosed in vitro on canine and porcine skin using a mixture-adjusted quantitative structure permeability relationship.

    PubMed

    Riviere, J E; Brooks, J D; Collard, W T; Deng, J; de Rose, G; Mahabir, S P; Merritt, D A; Marchiondo, A A

    2014-10-01

    Topical application of ectoparasiticides for flea and tick control is a major focus for product development in animal health. The objective of this work was to develop a quantitative structure permeability relationship (QSPeR) model sensitive to formulation effects for predicting absorption and skin deposition of five topically applied drugs administered in six vehicle combinations to porcine and canine skin in vitro. Saturated solutions (20 μL) of (14) C-labeled demiditraz, fipronil, permethrin, imidacloprid, or sisapronil were administered in single or binary (50:50 v/v) combinations of water, ethanol, and transcutol (6 formulations, n = 4-5 replicates per treatment) nonoccluded to 0.64 cm(2) disks of dermatomed pig or dog skin mounted in flow-through diffusion cells. Perfusate flux over 24 h and skin deposition at termination were determined. Permeability (logKp), absorption, and penetration endpoints were modeled using a four-term Abrahams and Martin (hydrogen-bond donor acidity and basicity, dipolarity/polarizability, and excess molar refractivity) linear free energy QSPeR equation with a mixture factor added to compensate for formulation ingredient interactions. Goodness of fit was judged by r(2) , cross-validation coefficient, coefficients (q(2) s), and Williams Plot to visualize the applicability domain. Formulation composition was the primary determinant of permeation. Compounds generally penetrated dog skin better than porcine skin. The vast majority of permeated penetrant was deposited within the dosed skin relative to transdermal flux, an attribute for ectoparasiticides. The best QSPeR logKp model for pig skin permeation (r(2) = 0.86, q(2) s = 0.85) included log octanol/water partition coefficient as the mixture factor, while for dogs (r(2) = 0.91, q(2) s = 0.90), it was log water solubility. These studies clearly showed that the permeation of topical ectoparasiticides could be well predicted using QSPeR models that account for both the physical

  9. Quantitative relationship among integrin-ligand binding, adhesion, and signaling via focal adhesion kinase and extracellular signal-regulated kinase 2.

    PubMed

    Asthagiri, A R; Nelson, C M; Horwitz, A F; Lauffenburger, D A

    1999-09-17

    Because integrin-mediated signals are transferred through a physical architecture and synergistic biochemical network whose properties are not well defined, quantitative relationships between extracellular integrin-ligand binding events and key intracellular responses are poorly understood. We begin to address this by quantifying integrin-mediated FAK and ERK2 responses in CHO cells for varied alpha(5)beta(1) expression level and substratum fibronectin density. Plating cells on fibronectin-coated surfaces initiated a transient, biphasic ERK2 response, the magnitude and kinetics of which depended on integrin-ligand binding properties. Whereas ERK2 activity initially increased with a rate proportional to integrin-ligand bond number for low fibronectin density, the desensitization rate was independent of integrin and fibronectin amount but proportional to the ERK2 activity level with an exponential decay constant of 0.3 (+/- 0.08) min(-1). Unlike the ERK2 activation time course, FAK phosphorylation followed a superficially disparate time course. However, analysis of the early kinetics of the two signals revealed them to be correlated. The initial rates of FAK and ERK2 signal generation exhibited similar dependence on fibronectin surface density, with both rates monotonically increasing with fibronectin amount until saturating at high fibronectin density. Because of this similar initial rate dependence on integrin-ligand bond formation, the disparity in their time courses is attributed to differences in feedback regulation of these signals. Whereas FAK phosphorylation increased to a steady-state level as new integrin-ligand bond formation continued during cell spreading, ERK2 activity was decoupled from the integrin-ligand stimulus and decayed back to a basal level. Accordingly, we propose different functional metrics for representing these two disparate dynamic signals: the steady-state tyrosine phosphorylation level for FAK and the integral of the pulse response for

  10. Kinetic Control of Aqueous Hydrolysis: Modulating Structure/Property Relationships in Inorganic Crystals

    NASA Astrophysics Data System (ADS)

    Neilson, James R.

    2011-12-01

    A grand challenge in materials science and chemistry revolves around the preparation of materials with desired properties by controlling structure on multiple length scales. Biology approaches this challenge by evolving tactics to transform soluble precursors into materials and composites with macro-scale and atomic precision. Studies of biomineralization in siliceous sponges led to the discovery of slow, catalytic hydrolysis of molecular precursors in the biogenesis of silica skeletal elements with well defined micro- and nano-scale architectures. However, the role of aqueous hydrolysis in the limit of kinetic control is not well understood; this allows us to form a central hypothesis: that the kinetics of hydrolysis modulate the structures of materials and their properties. As a model system, the diffusion of a simple hydrolytic catalyst (such as ammonia) across an air-water interface into a metal salt solution reproduces some aspects of the chemistry found in biomineralization, namely kinetic and vectorial control. Variation of the catalyst concentration modulates the hydrolysis rate, and thus alters the resulting structure of the inorganic crystals. Using aqueous solutions of cobalt(II) chloride, each product (cobalt hydroxide chloride) forms with a unique composition, despite being prepared from identical mother liquors. Synchrotron X-ray total scattering methods are needed to locate the atomic positions in the material, which are not aptly described by a traditional crystallographic unit cell due to structural disorder. Detailed definition of the structure confirms that the hydrolysis conditions systematically modulate the arrangement of atoms in the lattice. This tightly coupled control of crystal formation and knowledge of local and average structures of these materials provides insight into the unusual magnetic properties of these cobalt hydroxides. The compounds studied show significant and open magnetization loops with little variation with composition or structure, yet subtle and systematic changes in the mean-field spin interaction strength and spin entropy loss. Meanwhile, neutron powder diffraction reveals a fully compensated Ńeel state; a detailed analysis of the local structure defines the aperiodic clusters of polyhedra responsible for magnetic order. The rate of hydrolysis of metal precursors modulates the disposition of these polyhedral clusters. The strategy of kinetically controlling aqueous hydrolysis also extends to the formation of stoichiometrically ordered bimetallic crystals [MSn(OH)6], where the hydrolysis behavior for dissimilar metal cations must be controlled via counteranions or precursor selection. In the formation of these ordered double perovskite hydroxides, the rate of hydrolysis is held constant in the limit of kinetic control. Instead, the propensities of different cations to undergo controlled hydrolysis are probed by their ability to form ordered crystals. Collectively, these studies demonstrate how systematic variation in the kinetic conditions of materials preparation and the character of each solute control the structure and properties of materials, with a precision not attainable through traditional or near-equilibrium approaches.

  11. Selenium-Containing Fused Bicyclic Heterocycle Diselenolodiselenole: Field Effect Transistor Study and Structure-Property Relationship.

    PubMed

    Debnath, Sashi; Chithiravel, Sundaresan; Sharma, Sagar; Bedi, Anjan; Krishnamoorthy, Kothandam; Zade, Sanjio S

    2016-07-20

    The first application of the diselenolodiselenole (C4Se4) heterocycle as an active organic field effect transistor materials is demonstrated here. C4Se4 derivatives (2a-2d) were obtained by using a newly developed straightforward diselenocyclization protocol, which includes the reaction of diynes with selenium powder at elevated temperature. C4Se4 derivatives exhibit strong donor characteristics and planar structure (except 2d). The atomic force microscopic analysis and thin-film X-ray diffraction pattern of compounds 2a-2d indicated the formation of distinct crystalline films that contain large domains. A scanning electron microscopy study of compound 2b showed development of symmetrical grains with an average diameter of 150 nm. Interestingly, 2b exhibited superior hole mobility, approaching 0.027 cm(2) V(-1) s(-1) with a transconductance of 9.2 μS. This study correlate the effect of π-stacking, Se···Se intermolecular interaction, and planarity with the charge transport properties and performance in the field effect transistor devices. We have shown that the planarity in C4Se4 derivatives was achieved by varying the end groups attached to the C4Se4 core. In turn, optoelectronic properties can also be tuned for all these derivatives by end-group variation. PMID:27353123

  12. Investigating the structure-property relationship of aromatic-aliphatic polyamide/layered silicate hybrid films

    NASA Astrophysics Data System (ADS)

    Zulfiqar, Sonia; Sarwar, Muhammad Ilyas

    2009-07-01

    Surface treated montmorillonite was used to prepare nanocomposites with aromatic-aliphatic polyamide by solution intercalation technique. The polyamide chains were produced through polycondensation of 4-aminophenyl sulfone with sebacoyl chloride in dimethyl acetamide. Compatibility between the polymer and organoclay was achieved through carbonyl chloride end-capped amide chains prepared by adding extra sebacoyl chloride near the end of polymerization reaction. The nanocomposites morphology and clay dispersion were investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Delaminated and intercalated morphologies were observed for different loading of organoclay. Tensile strength and modulus improved for nanocomposites with optimum organoclay content (10-wt.%). Thermal stability and glass transition temperature of nanocomposites increased relative to pristine polyamide with augmenting organoclay content. Water uptake of these materials decreased as compared to the neat polyamide indicating reduced permeability.

  13. The Structure-Property Relationship of Poly(amide-imide)/Organoclay Nanocomposites

    NASA Astrophysics Data System (ADS)

    Faghihi, Khalil; Soleimani, Masoumeh; Shabanian, Meisam; Abootalebi, Ashraf Sadateh

    2011-06-01

    Surface treated montmorillonite (MMT) was used to prepare nanocomposites with poly(amide-imide) (PAI) 5 by solution intercalation technique with various percent of organoclay (5-15 mass %). Surface modification of the MMT was performed with Cloisite 20A for ample compatibilization with the PAI matrix. The PAI 5 chains were produced through polycondensation of 4,4-diamino diphenyl sulfone 4 with N-trimellitylimido-L-alanine 3 in a medium consisting of triphenyl phosphite, N-methyl-2-pyrolidone (NMP), pyridine and calcium chloride. The PAI-Nanocomposites morphology and clay dispersion were investigated by X-ray diffraction (XRD) and Scanning electron microscopy (SEM). The effect of clay dispersion and the interaction between clay and PAI chains on the properties of PAI-Nanocomposites films were investigated by using UV-Vis spectroscopy, thermogravimetric analysis (TGA) and water uptake measurements. Thermal stability of nanocomposites increased relative to the neat polyamide with increasing organoclay content but water uptake of these materials decreased as compared to the neat polyamide indicating reduced permeability.

  14. Relationship of the optical absorption and scattering properties with mechanical and structural properties of apple tissue

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Optical absorption and scattering properties of fruit change with the physiological and biochemical activities in the tissue during ripening and postharvest storage. But it has not been well understood on how these changes are related to the structural and mechanical properties of fruit. This resear...

  15. Structure-Property Relationships of Inorganically Surface-Modified Zeolite Molecular Sieves for Nanocomposite Membrane Fabrication

    SciTech Connect

    Lydon, Megan E; Unocic, Kinga A; Jones, Christopher W; Nair, Sankar

    2012-01-01

    A multiscale experimental study of the structural, compositional, and morphological characteristics of aluminosilicate (LTA) and pure-silica (MFI) zeolite materials surface-modified with MgO{sub x}H{sub y} nanostructures is presented. These characteristics are correlated with the suitability of such materials in the fabrication of LTA/Matrimid mixed-matrix membranes (MMMs) for CO{sub 2}/CH{sub 4} separations. The four functionalization methods studied in this work produce surface nanostructures that may appear superficially similar under SEM observation but in fact differ considerably in shape, size, surface coverage, surface area/roughness, degree of attachment to the zeolite surface, and degree of zeolite pore blocking. The evaluation of these characteristics by a combination of TEM, HRTEM, N{sub 2} physisorption, multiscale compositional analysis (XPS, EDX, and ICP-AES elemental analysis), and diffraction (ED and XRD) allows improved understanding of the origin of disparate gas permeation properties observed in MMMs made with four types of surface-modified zeolite LTA materials, as well as a rational selection of the method expected to result in the best enhancement of the desired properties (in the present case, CO{sub 2}/CH{sub 4} selectivity increase without sacrificing permeability). A method based on ion exchange of the LTA with Mg{sup 2+}, followed by base-induced precipitation and growth of MgOxHy nanostructures, deemed 'ion exchange functionalization' here, offers modified particles with the best overall characteristics resulting in the most effective MMMs. LTA/Matrimid MMMs containing ion exchange functionalized particles had a considerably higher CO{sub 2}/CH{sub 4} selectivity (40) than could be obtained with the other functionalization techniques (30), while maintaining a CO{sub 2} permeability of 10 barrers. A parallel study on pure silica MFI surface nanostructures is also presented to compare and contrast with the zeolite LTA case.

  16. Electroformed iron as new biomaterial for degradable stents: development process and structure-properties relationship.

    PubMed

    Moravej, M; Prima, F; Fiset, M; Mantovani, D

    2010-05-01

    An electroforming technique was developed for fabricating iron foils targeted for application as biodegradable cardiovascular stent material. The microstructure, mechanical properties and corrosion of electroformed iron (E-Fe) foils were evaluated and compared with those of pure iron made by casting and thermomechanical treatment (CTT-Fe), with 316L stainless steel (316L SS) and with other candidate metallic materials for biodegradable stents. Electron backscattered diffraction revealed an average grain size of 4 microm for E-Fe, resulting in a high yield (360 MPa) and ultimate tensile strength (423 MPa) being superior to those of other metallic biodegradable stent materials. Annealing at 550 degrees C was found to improve the ductility of the E-Fe from 8% to 18%. The corrosion rate of E-Fe in Hanks' solution, measured by potentiodynamic polarization, was higher than that of CTT-Fe, which had been found to have a slow in vivo degradation. The results showed that E-Fe possesses fine-grain microstructure, suitable mechanical properties and moderate corrosion rate as a degradable stent material. PMID:20085829

  17. Structure-property relationships in thermomechanically treated beryllia dispersed nickel alloys

    NASA Technical Reports Server (NTRS)

    Grewal, M. S.; Sastri, S. A.; Grant, N. J.

    1975-01-01

    BeO dispersed nickel alloys, produced by powder metallurgy techniques, were studied extensively in stress rupture at 815, 982, and 1093 C (1088, 1255, and 1366 K) and by transmission electron microscopy. The alloys were subjected to a variety of thermomechanical treatments (TMT) to determine the benefits of TMT on properties. It is shown that the use of intermediate annealing treatments after 10 pct reduction steps is highly beneficial on both low and high temperature properties. It is indicated that the high temperature strength is not primarily dependent on the grain aspect ratio or texture but depends strongly on the dislocation density and distribution of dislocations in a stable substructure which is pinned by the fine oxide dispersion.

  18. Novel multiphase systems based on thermoplastic chitosan: Analysis of the structure-properties relationships

    NASA Astrophysics Data System (ADS)

    Avérous, Luc; Pollet, Eric

    2016-03-01

    In the last years, biopolymers have attracted great attention. It is for instance the case of chitosan, a linear polysaccharide. It is a deacetylated derivative of chitin, which is the second most abundant polysaccharide found in nature after cellulose. Chitosan has been found to be nontoxic, biodegradable, biofunctional, and biocompatible in addition to having antimicrobial and antifungal properties, and thus has a great potential for environmental (packaging,) or biomedical applications.For preparing chitosan-based materials, only solution casting or similar methods have been used in all the past studies. Solution casting have the disadvantage in low efficiency and difficulty in scaling-up towards industrial applications. Besides, a great amount of environmentally unfriendly chemical solvents are used and released to the environment in this method. The reason for not using a melt processing method like extrusion or kneading in the past studies is that chitosan, like many other polysaccharides such as starch, has very low thermal stability and degrade prior to melting. Therefore, even if the melt processing method is more convenient and highly preferred for industrial production, its adaptation for polysaccharide-based materials remains very difficult. However, our recently published studies has demonstrated the successful use of an innovative melt processing method (internal mixer, extrusion,) as an alternative route to solution casting, for preparing materials based on thermoplastic chitosan. These promising thermoplastic materials, obtained by melt processing, have been the main topic of recent international projects, with partners from different countries Multiphase systems based on various renewable plasticizers have been elaborated and studied. Besides, different blends, and nano-biocomposites based on nanoclays, have been elaborated and fully analyzed. The initial consortium of this vast project was based on an international consortium (Canada, Australia, France). This project is currently ongoing and open, with new international academic partners (Mexico, Brazil and Spain).

  19. Investigation of structure-property relationships in systematic series of novel polymers

    NASA Technical Reports Server (NTRS)

    Gillham, J. K.

    1976-01-01

    Solid state transitions in polymeric materials was associated with the onset of sub-molecular motions of the polymer chains. Although these were considered to be intramolecular in general, the local environment of the polymer molecule exerts a strong influence through, for example, the effects of crystallinity, polarity and diluents. The manner of specimen preparation and previous history also affect transitions. The transitions are considered to arise when sufficient free volume is available to permit the occurrence of these side chain and backbone reorientations. The glass transition is the principal transition of amorphous polymeric materials and is associated with the onset of long range segmental motion of the polymer backbone. The various types of shorter range motion occurring below the glass transition have been catalogued.

  20. Structure-property relationships for self-assembled zinc chlorin light-harvesting dye aggregates.

    PubMed

    Huber, Valerie; Sengupta, Sanchita; Würthner, Frank

    2008-01-01

    A series of zinc 3(1)-hydroxymethyl chlorins 10 a-e and zinc 3(1)-hydroxyethyl chlorins 17 with varied structural features were synthesized by modifying naturally occurring chlorophyll a. Solvent-, temperature-, and concentration-dependent UV/Vis and CD spectroscopic methods as well as microscopic investigations were performed to explore the importance of particular functional groups and steric effects on the self-assembly behavior of these zinc chlorins. Semisynthetic zinc chlorins 10 a-e possess the three functional units relevant for self-assembly found in their natural bacteriochlorophyll (BChl) counterparts, namely, the 3(1)-OH group, a central metal ion, and the 13(1) C==O moiety along the Qy axis, and they contain various 17(2)-substituents. Depending on whether the zinc chlorins have 17(2)-hydrophobic or hydrophilic side chains, they self-assemble in nonpolar organic solvents or in aqueous media, respectively. Zinc chlorins possessing at least two long side chains provide soluble self-aggregates that are stable in solution for a prolonged time, thus facilitating elucidation of their properties by optical spectroscopy. The morphology of the zinc chlorin aggregates was elucidated by atomic force microscopy (AFM) studies, revealing well-defined nanoscale rod structures for zinc chlorin 10 b with a height of about 6 nm. It is worth noting that this size is in good accordance with a tubular arrangement of the dyes similar to that observed in their natural BChl counterparts in the light-harvesting chlorosomes of green bacteria. Furthermore, for the epimeric 3(1)-hydroxyethyl zinc chlorins 17 with hydrophobic side chains, the influence of the chirality center at the 3(1)-position on the aggregation behavior was studied in detail by UV/Vis and CD spectroscopy. Unlike zinc chlorins 10, the 3(1)-hydroxyethyl zinc chlorins 17 formed only small oligomers and not higher rod aggregate structures, which can be attributed to the steric effect imposed by the additional methyl group at the 3(1)-position. PMID:18642260

  1. Structure-property relationships in Waspaloy via small angle scattering and electrical resistivity measurements

    SciTech Connect

    Whelchel, R.; Gerhardt, Dr. Rosario; Littrell, Ken

    2010-01-01

    The mechanical properties in superalloys are controlled by the distribution of the {gamma}{prime} precipitate phase. Electrical measurements have been shown to be sensitive to certain aspects of the precipitation process and show promise for predicting the evolving microstructural state in superalloys. Aging experiments were conducted on Waspaloy samples for temperatures between 600 and 950 C for times ranging from 2min to 500h. Particle size distributions were obtained by modeling of small angle scattering (SAS) data, whereas, small precipitate size information, strain, and lattice mismatch data were obtained from X-ray diffraction. The microstructural information was then used to create a figure of merit of electron scattering intended to correlate electrical properties to the precipitate microstructure. The proposed figure of merit shows an empirical correlation with the electrical resistivity data, demonstrating the sensitivity of the resistivity measurements to the precipitation process and coarsening behavior.

  2. A density functional theory study of structure-property relationships for Pt-Ni alloy catalysts

    NASA Astrophysics Data System (ADS)

    Cao, Liang; Mueller, Tim

    2013-03-01

    The ORR (Oxygen Reduction Reaction) is an important reaction in devices such as metal-air batteries and PEMFCs (Polymer Electrolyte Membrane fuel cells). Pure Pt is one of the most successful electrode catalysts for this key reaction. However, due to its expense, numerous efforts have been made to find a new catalysis system based on Pt bimetallic alloys, in which Pt is partially replaced by less expensive metals, such as Ni, Co and Fe. Experimental and theoretical works have shown that Pt3Ni alloys have a higher ORR activity than pure Pt. In order to investigate the enhanced catalytic activity, cluster expansions corresponding to a simplified 9-layer Pt-Ni slab model are built to accurately and quickly predict the energies of surfaces as a function of atomic order. With the help of this model, we can study systematically the atomic structure and the surface geometry of Pt3Ni surface system at a variety of temperature and chemical environments, and we can calculate the adsorption binding energies of O, OH and H on both equilibrium and non-equilibrium Pt-Ni(111) surfaces. Also, we can investigate the effects of off-stoichiometry on surface by searching for stable ground states under different concentrations.

  3. Structure-Property Relationships of Poly(lactide)-based Triblock and Multiblock Copolymers

    NASA Astrophysics Data System (ADS)

    Panthani, Tessie Rose

    Replacing petroleum-based plastics with alternatives that are degradable and synthesized from annually renewable feedstocks is a critical goal for the polymer industry. Achieving this goal requires the development of sustainable analogs to commodity plastics which have equivalent or superior properties (e.g. mechanical, thermal, optical etc.) compared to their petroleum-based counterparts. This work focuses on improving and modulating the properties of a specific sustainable polymer, poly(lactide) (PLA), by incorporating it into triblock and multiblock copolymer architectures. The multiblock copolymers in this work are synthesized directly from dihydroxy-terminated triblock copolymers by a simple step-growth approach: the triblock copolymer serves as a macromonomer and addition of stoichiometric quantities of either an acid chloride or diisocyanate results in a multiblock copolymer. This work shows that over wide range of compositions, PLA-based multiblock copolymers have superior mechanical properties compared to triblock copolymers with equivalent chemical compositions and morphologies. The connectivity of the blocks within the multiblock copolymers has other interesting consequences on properties. For example, when crystallizable poly(L-lactide)-based triblock and multiblock copolymers are investigated, it is found that the multiblock copolymers have much slower crystallization kinetics. Additionally, the total number of blocks connected together is found to effect the linear viscoelastic properties as well as the alignment of lamellar domains under uniaxial extension. Finally, the synthesis and characterization of pressure-sensitive adhesives based upon renewable PLA-containing triblock copolymers and a renewable tackifier is detailed. Together, the results give insight into the effect of chain architecture, composition, and morphology on the mechanical behavior, thermal properties, and rheological properties of PLA-based materials.

  4. Structure-property relationships of iron-hydroxyapatite ceramic matrix nanocomposite fabricated using mechanosynthesis method.

    PubMed

    Nordin, Jamillah Amer; Prajitno, Djoko Hadi; Saidin, Syafiqah; Nur, Hadi; Hermawan, Hendra

    2015-06-01

    Hydroxyapatite (HAp) is an attractive bioceramics due to its similar composition to bone mineral and its ability to promote bone-implant interaction. However, its low strength has limited its application as load bearing implants. This paper presented a work focusing on the improvement of HAp mechanical property by synthesizing iron (Fe)-reinforced bovine HAp nanocomposite powders via mechanosynthesis method. The synthesis process was performed using high energy milling at varied milling time (3, 6, 9, and 12h). The samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), and scanning electron microscopy (SEM). Its mechanical properties were investigated by micro-Vicker's hardness and compression tests. Results showed that milling time directly influenced the characteristics of the nanocomposite powders. Amorphous BHAp was formed after 9 and 12h milling in the presence of HPO4(2-) ions. Continuous milling has improved the crystallinity of Fe without changing the HAp lattice structure. The nanocomposite powders were found in spherical shape, agglomerated and dense after longer milling time. The hardness and Young's modulus of the nanocomposites were also increased at 69% and 66%, respectively, as the milling time was prolonged from 3 to 12h. Therefore, the improvement of the mechanical properties of nanocomposite was attributed to high Fe crystallinity and homogenous, dense structure produced by mechanosynthesis. PMID:25842138

  5. Structure-property relationship of metal-organic frameworks (MOFs) and physisorbed off-gas radionuclides.

    SciTech Connect

    Nenoff, Tina Maria; Chupas, Peter J.; Garino, Terry J.; Rodriguez, Mark Andrew; Chapman, Karena W.; Sava, Dorina Florentina

    2010-11-01

    We report on the host-guest interactions between metal-organic frameworks (MOFs) with various profiles and highly polarizable molecules (iodine), with emphasis on identifying preferential sorption sites in these systems. Radioactive iodine 129I, along with other volatile radionuclides (3H, 14C, Xe and Kr), represents a relevant component in the off-gas resulted during nuclear fuel reprocessing. Due to its very long half-life, 15.7 x 106 years, and potential health risks in humans, its efficient capture and long-term storage is of great importance. The leading iodine capture technology to date is based on trapping iodine in silver-exchanged mordenite. Our interests are directed towards improving existent capturing technologies, along with developing novel materials and alternative waste forms. Herein we report the first study that systematically monitors iodine loading onto MOFs, an emerging new class of porous solid-state materials. In this context, MOFs are of particular interest as: (i) they serve as ideal high capacity storage media, (ii) they hold potential for the selective adsorption from complex streams, due to their high versatility and tunability. This work highlights studies on both newly developed in our lab, and known highly porous MOFs that all possess distinct characteristics (specific surface area, pore volume, pore size, and dimension of the window access to the pore). The materials were loaded to saturation, where elemental iodine was introduced from solution, as well as from vapor phase. Uptakes in the range of {approx}125-150 wt% I2 sorbed were achieved, indicating that these materials outperform all other solid adsorbents to date in terms of overall capacity. Additionally, the loaded materials can be efficiently encapsulated in stable waste forms, including as low temperature sintering glasses. Ongoing studies are focused on gathering qualitative information with respect to localizing the physisorbed iodine molecules within the frameworks: X-ray single-crystal analyses, in conjunction with high pressure differential pair distribution function (d-PDF) studies aimed to identify preferential sites in the pores, and improve MOFs robustness. Furthermore, durability studies on the iodine loaded MOFs and subsequent waste forms include thermal analyses, SEM/EDS elemental mapping, and leach-durability testing. We anticipate for this in-depth analysis to further aid the design of advanced materials, capable to address major hallmarks: safe capture, stability and durability over extended timeframes.

  6. The structure-property relationships of powder processed Fe-Al-Si alloys

    NASA Astrophysics Data System (ADS)

    Prichard, Paul Dehnhardt

    Iron-aluminum alloys have been extensively evaluated as semi-continuous product such as sheet and bar, but have not been evaluated by net shape PN processing techniques such as metal injection molding. The alloy compositions of iron-aluminum alloys have been optimized for room temperature ductility, but have limited high temperature strength. Hot extruded powder alloys in the Fe-Al-Si system have developed impressive mechanical properties, but the effects of sintering on mechanical properties have not been explored. This investigation evaluated three powder processed Fe-Al-Si alloys: Fe-15Al, Fe-15Al-2.8Si, Fe-15Al-5Si (atomic%). The powder alloys were produced with a high pressure gas atomization (HPGA) process to obtain a high fraction of metal injection molding (MIM) quality powder (Dsb{84} < 32μm). The powders were consolidated either by P/M hot extrusion or by vacuum sintering. The extruded materials were near full density with grain sizes ranging from 30 to 50 mum. The vacuum sintering conditions produced samples with density ranging from 87% to 99% of theoretical density, with an average grain size ranging from 26 mum to 104 mum. Mechanical property testing was conducted on both extruded and sintered material using small punch test. Tensile tests were conducted on extruded bar for comparison with the punch test data. Punch tests were conducted from 25sp°C to 550sp°C to determine the yield strength, and fracture energy for each alloy as a function of processing condition. The ductile to brittle transition temperature (DBTT) was observed to increase with an increasing silicon content. The Fe-15Al-2.8Si alloy was selected for more extensive testing due to the combination of high temperature strength and low temperature toughness due to the two phase alpha + DOsb3 structure. The extruded material developed higher yield strength at temperatures below the DBTT, but the sintered material developed higher strengths above the DBTT. The fracture energy of these alloys was higher at all test temperatures, which indicated the importance of grain size and pore interaction with crack propagation. This investigation provided a framework for understanding the effects of silicon in powder processing and mechanical property behavior of Fe-Al-Si alloys.

  7. Water Transport Polymers -- Structure/Property Relationships of a Series of Phosphazene Polymers

    SciTech Connect

    Christopher J. Orme; Eric S. Peterson; William F. Bauer; Frederick F. Stewart; Mason K. Harrup; Thomas A. Luther; John R. Klaehn; John E. Wey

    2010-01-01

    A study was undertaken to explore the water passing properties of a series of phosphazene polymers versus attached pendant group structure. Pendant groups containing different numbers ethyleneoxy groups were synthetically attached to the backbone of phosphazene polymers. Phosphazene polymers facilitate these types of studies because during their synthesis the polymer backbone is formed first and then the desired pendant groups are attached through nucleophilic substitution. For these studies, four polymer series were synthesized and tested for their water passing properties. The polymers contained different amounts of ethyleneoxy units. Two polymer families were synthesized and compared in this work. The critical difference in these two series is that one contained pendant groups with aromatic rings, in addition to the oligioethyleneoxy moieties, while the other does not. Polymers with phenyl group-containing pendant groups exhibited poor water permeability if they possessed fewer than six ethyleneoxy units. Polymers with more than six ethyleneoxy units inserted between the phenyl ring (tail) and the polymeric backbone, exhibited reasonable water permeability. Two additional series of mixed pendant group polymers were synthesized and the water passing properties of the phosphazenes varied in proportion to the hydrophilic to hydrophobic balance induced by each individual pendant group. A final study, polymers with shorter pendant groups, is shown to fully demonstrate the effect of pendant group on water permeability. These studies suggest that the polyphosphazenes may be tailored for specific water passing applications.

  8. Structure/property relationships in methacrylate/dimethacrylate polymers for dental applications

    NASA Astrophysics Data System (ADS)

    Mehlem, Jeremy John

    Since its invention Bis-GMA or one of its analogs has been the main component of the polymer portion of composites for dental restorations. The need for dilution of Bis-GMA and its analogs to optimize its properties has long been recognized. Bis-GMA is a highly viscous monomer. This high viscosity leads to early vitrification, which limits conversion during cure. This viscosity also limits filler loading. Vitrification at low conversions leads to heterogeneous systems composed of low and high cross-link density phases. The low cross-link density phases behave as defects in the system; therefore, if the amount of low cross-link density phases in the system can be reduced and a more uniform network structure can be achieved, then the mechanical properties of the resin can be improved. Since the increase in viscosity during cure causes vitrification, it is logical that a system with a low initial viscosity will delay the onset of vitrification. Reactive diluents such as triethylene glycol dimethacrylate (TEGDMA) are effective at lower levels. However, large amounts negatively affect matrix properties by increasing polymerization shrinkage and water sorption. Shrinkage has been cited as one of the main deficiencies in dental composites. The goal of this project is to improve upon standard viscosity modifying comonomers such as triethylene glycol dimethacrylate. The comonomers that were explored were phenyloxyethyl methacrylate, cyclohexyl methacrylate, and tert-butylcylcohexyl methacrylate. Multicomponent systems based on analogs of ethylene glycol dimethacrylates with different length ethyl glycol chains were also examined. The substitution of monomethacrylates for TEGDMA as a comonomer resulted in enhanced or negligible affects on the mechanical properties of Bis-MEPP based polymer systems while reducing polymerization shrinkage. 129Xenon NMR and TappingMode(TM) AFM were used to characterize the heterogeneity of dimethacrylates systems during their cure cycle as well as in their final state. Using these methods the size of the high and low cross-link density phase was examined and determined to be on the order of 50--150 nanometers. Model compounds based on phenylethyl methacrylate were formulated to determine how of nadic methyl anhydride and maleic anhydride incorporate into dimethacrylate resin systems.

  9. Structure-property relationships in low-temperature adhesives. [for inflatable structures

    NASA Technical Reports Server (NTRS)

    Schoff, C. K.; Udipi, K.; Gillham, J. K.

    1977-01-01

    Adhesive materials of aliphatic polyester, linear hydroxyl end-capped polybutadienes, or SBS block copolymers are studied with the objective to replace conventional partially aromatic end-reactive polyester-isocyanate adhesives that have shown embrittlement

  10. Structure Property Relationship of Suspension Thermally Sprayed WC-Co Nanocomposite Coatings

    NASA Astrophysics Data System (ADS)

    Ahmed, R.; Faisal, N. H.; Al-Anazi, Nayef M.; Al-Mutairi, S.; Toma, F.-L.; Berger, L.-M.; Potthoff, A.; Polychroniadis, E. K.; Sall, M.; Chaliampalias, D.; Goosen, M. F. A.

    2015-02-01

    Tribomechanical properties of nanostructured coatings deposited by suspension high velocity oxy-fuel (S-HVOF) and conventional HVOF (Jet Kote) spraying were evaluated. Nanostructured S-HVOF coatings were obtained via ball milling of the agglomerated and sintered WC-12Co feedstock powder, which were deposited via an aqueous-based suspension using modified HVOF (TopGun) process. Microstructural evaluations of these hardmetal coatings included transmission electron microscopy, x-ray diffraction, and scanning electron microscopy equipped with energy dispersive x-ray spectroscopy. The nanohardness and modulus of the coated specimens were investigated using a diamond Berkovich nanoindenter. Sliding wear tests were conducted using a ball-on-flat test rig. Results indicated that low porosity coatings with nanostructured features were obtained. High carbon loss was observed, but coatings showed a high hardness up to 1000 HV2.9N. S-HVOF coatings also showed improved sliding wear and friction behavior, which were attributed to nanosized particles reducing ball wear in three-body abrasion and support of metal matrix due to uniform distribution of nanoparticles in the coating microstructure.

  11. Structure-property-glass transition relationships in non-isocyanate polyurethanes investigated by dynamic nanoindentation

    NASA Astrophysics Data System (ADS)

    Weyand, Stephan; Blattmann, Hannes; Schimpf, Vitalij; Mülhaupt, Rolf; Schwaiger, Ruth

    2016-07-01

    Newly developed green-chemistry approaches towards the synthesis of non-isocyanate polyurethane (NIPU) systems represent a promising alternative to polyurethanes (PU) eliminating the need for harmful ingredients. A series of NIPU systems were studied using different nanoindentation techniques in order to understand the influence of molecular parameters on the mechanical behavior. Nanoindentation revealed a unique characteristic feature of those materials, i.e. stiffening with increasing deformation. It is argued that the origin of this observed stiffening is a consequence of the thermodynamic state of the polymer network, the molecular characteristics of the chemical building blocks and resulting anisotropic elastic response of the network structure. Flat-punch nanoindentation was applied in order to characterize the constitutive viscoelastic nature of the materials. The complex modulus shows distinct changes as a function of the NIPU network topology illustrating the influence of the chemical building blocks. The reproducibility of the data indicates that the materials are homogeneous over the volumes sampled by nanoindentation. Our study demonstrates that nanoindentation is very well-suited to investigate the molecular characteristics of NIPU materials that cannot be quantified in conventional experiments. Moreover, the technique provides insight into the functional significance of complex molecular architectures thereby supporting the development of NIPU materials with tailored properties.

  12. The structure-property relationships of powder processed Fe-Al-Si alloys

    SciTech Connect

    Prichard, P.D.

    1998-02-23

    Iron-aluminum alloys have been extensively evaluated as semi-continuous product such as sheet and bar, but have not been evaluated by net shape P/M processing techniques such as metal injection molding. The alloy compositions of iron-aluminum alloys have been optimized for room temperature ductility, but have limited high temperature strength. Hot extruded powder alloys in the Fe-Al-Si system have developed impressive mechanical properties, but the effects of sintering on mechanical properties have not been explored. This investigation evaluated three powder processed Fe-Al-Si alloys: Fe-15Al, Fe-15Al-2.8Si, Fe-15Al-5Si (atomic %). The powder alloys were produced with a high pressure gas atomization (HPGA) process to obtain a high fraction of metal injection molding (MIM) quality powder (D{sub 84} < 32 {micro}m). The powders were consolidated either by P/M hot extrusion or by vacuum sintering. The extruded materials were near full density with grain sizes ranging from 30 to 50 {micro}m. The vacuum sintering conditions produced samples with density ranging from 87% to 99% of theoretical density, with an average grain size ranging from 26 {micro}m to 104 {micro}m. Mechanical property testing was conducted on both extruded and sintered material using a small punch test. Tensile tests were conducted on extruded bar for comparison with the punch test data. Punch tests were conducted from 25 to 550 C to determine the yield strength, and fracture energy for each alloy as a function of processing condition. The ductile to brittle transition temperature (DBTT) was observed to increase with an increasing silicon content. The Fe-15Al-2.8Si alloy was selected for more extensive testing due to the combination of high temperature strength and low temperature toughness due to the two phase {alpha} + DO{sub 3} structure. This investigation provided a framework for understanding the effects of silicon in powder processing and mechanical property behavior of Fe-Al-Si alloys.

  13. New Synthetic Methods and Structure-Property Relationships in Neptunium, Plutonium, and Americium Borates. Final report

    SciTech Connect

    Albrecht-Schmitt, Thomas Edward

    2013-09-14

    The past three years of support by the Heavy Elements Chemistry Program have been highly productive in terms of advanced degrees awarded, currently supported graduate students, peer-reviewed publications, and presentations made at universities, national laboratories, and at international conferences. Ph.D. degrees were granted to Shuao Wang and Juan Diwu, who both went on to post-doctoral appointments at the Glenn T. Seaborg Center at Lawrence Berkeley National Laboratory with Jeff Long and Ken Raymond, respectively. Pius Adelani completed his Ph.D. with me and is now a post-doc with Peter C. Burns. Andrea Alsobrook finished her Ph.D. and is now a post-doc at Savannah River with Dave Hobbs. Anna Nelson completed her Ph.D. and is now a post-doc with Rod Ewing at the University of Michigan. As can be gleaned from this list, students supported by the Heavy Elements Chemistry grant have remained interested in actinide science after leaving my program. This follows in line with previous graduates in this program such as Richard E. Sykora, who did his post-doctoral work at Oak Ridge National Laboratory with R. G. Haire, and Amanda C. Bean, who is a staff scientist at Los Alamos National Laboratory, and Philip M. Almond and Thomas C. Shehee, who are both staff scientists at Savannah River National Laboratory, Gengbang Jin who is a staff scientist at Argonne National Lab, and Travis Bray who has been a post-doc at both LBNL and ANL. Clearly this program is serving as a pipe-line for students to enter into careers in the national laboratories. About half of my students depart the DOE complex for academia or industry. My undergraduate researchers also remain active in actinide chemistry after leaving my group. Dan Wells was a productive undergraduate of mine, and went on to pursue a Ph.D. on uranium and neptunium chalcogenides with Jim Ibers at Northwestern. After earning his Ph.D., he went directly into the nuclear industry.

  14. Structure-property relationships of an electron beam cured model urethane prepolymer

    SciTech Connect

    Joseph, E.; Wilkes, G.; Park, K.

    1981-10-01

    A semicrystalline urethane prepolymer derived from polycaprolactone was crosslinked below and above the melt to different levels using electron beam radiation. Studies at room temperature on the systems crosslinked under ambient conditions, which is below the melting temperature, show that changes in mechanical properties which occur as the electron beam dose is increased are due principally to the increase in crosslink density and to the changes in the crosslinking mechanism. Specifically, crosslinking takes place mainly at the acrylate double bonds or may also occur along the polymer backbone. All systems, however, are semicrystalline and possess a spherulitic texture. Mechanical and rheo-optical testing above the melt on these same systems indicate that at extensions up to 125% classical rubber elasticity theory and photoelasticity theory is obeyed. Isothermal crystallization kinetics measurements show that the rate of crystallization decreases as the electron beam dose is raised. When the systems are crosslinked above the melt again a spherulitic texture results. Mechanical testing above the melting temperature on the prepolymer crosslinked up to 4 Mrad shows that at elongations up to 125% classical rubber elasticity theory is obeyed. At room temperature these latter crosslinked systems exhibited a lower modulus compared to the materials crosslinked below the melt. Polarizing optical microscopy carried out above the melting temperature strongly suggested that no order was present in these systems during crosslinking in contrast to those crosslinked below the melting temperature.

  15. Structure-property-composition relationships in doped zinc oxides: enhanced photocatalytic activity with rare earth dopants.

    PubMed

    Goodall, Josephine B M; Illsley, Derek; Lines, Robert; Makwana, Neel M; Darr, Jawwad A

    2015-02-01

    In this paper, we demonstrate the use of continuous hydrothermal flow synthesis (CHFS) technology to rapidly produce a library of 56 crystalline (doped) zinc oxide nanopowders and two undoped samples, each with different particle properties. Each sample was produced in series from the mixing of an aqueous stream of basic zinc nitrate (and dopant ion or modifier) solution with a flow of superheated water (at 450 °C and 24.1 MPa), whereupon a crystalline nanoparticle slurry was rapidly formed. Each composition was collected in series, cleaned, freeze-dried, and then characterized using analytical methods, including powder X-ray diffraction, transmission electron microscopy, Brunauer-Emmett-Teller surface area measurement, X-ray photoelectron spectroscopy, and UV-vis spectrophotometry. Photocatalytic activity of the samples toward the decolorization of methylene blue dye was assessed, and the results revealed that transition metal dopants tended to reduce the photoactivity while rare earth ions, in general, increased the photocatalytic activity. In general, low dopant concentrations were more beneficial to having greater photodecolorization in all cases. PMID:25602735

  16. Multiple Quantum NMR Investigations of Structure- Property Relationships in Synthetic and Aged Silicone Elastomers

    SciTech Connect

    Maxwell, R; Gjersing, E; Chinn, S; Herberg, J; Eastwood, E; Bowen, D; Stephens, T

    2006-09-27

    Complex engineering elastomeric materials are often characterized by a complex network structure obtained by crosslinking network chains with multiple chain lengths. Further, these networks are commonly filled with thixotropic reinforcing agents such as SiO{sub 2} or carbon black. Degradation of such materials often occurs via mechanisms that alter the fundamental network structure. In order to understand the effects of modifications of network structure and filler-polymer interaction on component performance, a series of model compounds have been studied by {sup 1}H multiple quantum NMR analysis and traditional mechanical property assessments. The {sup 1}H NMR data provides insight into the distribution of segmental dynamics that reveals insight into the changes in mechanical properties.

  17. Structure-property relationships in flavour-barrier membranes with reduced high-temperature diffusivity

    SciTech Connect

    Heitfeld, Kevin A.; Schaefer, Dale W.

    2010-10-12

    Encapsulation is used to decrease the premature release of volatile flavour ingredients while offering protection against environmental damage such as oxidation, light-induced reactions, etc. Hydroxypropyl cellulose (HPC) is investigated here as a 'smart,' temperature responsive membrane for flavour encapsulation and delivery. Gel films were synthesized and characterized by diffusion and small-angle neutron and X-ray scattering techniques. Increasing temperature typically increases the diffusion rate across a membrane; HPC, however, can be tailored to give substantially improved elevated temperature properties. Scattering results indicate processing conditions have a significant impact on membrane morphology (micro phase separation). Under certain synthetic conditions, micro phase separation is mitigated and the membranes show temperature-independent diffusivity between 25 C and 60 C.

  18. Structure-property-relationship of p-toluidinium tetrachloromercurate(II)

    SciTech Connect

    Dinesh; Kumar, Mukesh; Dalela, S.

    2014-04-24

    The single crystals of p-toluidinium tetrachloromercurate(II) hybrid materials have been grown with perfect crystal of size 0.35 × 0.30 × 0.27 mm. The hybrid material is exposed to X-rays for 3D intensity data which is used to refine the crystal structure upto reliability-factor of 0.034. The phenyl ring has planar conformation with skeletal torsion angle of 0.003(6)° and the aromatic ring (C1-C6) forms an angle of 78.7(1)° to the plane of inorganic layer. The N-H...Cl hydrogen bonded tetramer pattern is observed in p-toluidinium tetrachloromercurate(II) and the two tetramer layers are separated by a distance of 3.925(6)Å and the minimum distance between two mercury atoms is 4.112(1)Å which is quite larger for any metallophilic interaction. The inorganic layers form zig-zag ribbons which are separated by a distance of 12.987(5)Å.

  19. Composition-structure-property-performance relationship inMn-substituted LiMn2O4

    SciTech Connect

    Horne, Craig R.; Richardson, Thomas J.; Gee, B.; Tucker, Mike; Grush, Melissa M.; Bergmann, Uwe; Striebel, Kathryn A.; Cramer, StephenP.; Reimer, Jeffrey A.; Cairns, Elton J.

    2001-03-09

    The spinel LiMn{sub 2}O{sub 4} has been extensively studied as a positive electrode active material in lithium rechargeable batteries. Partial substitution of Mn by another metal has also been the subject of recent study in an effort to improve the cycling performance. In general, the literature has shown that Mn substitution results in improved cycling stability at the expense of capacity (1,2). Resistance to the formation of tetragonal phase upon lithiation of the starting spinel (via a higher nominal Mn oxidation state in the substituted spinel) has been suggested as a mechanism for the improved performance. The degree of substitution is an important factor to optimize in order to minimize capacity loss and costs. The spectroscopic investigations on LiMn{sub 2}O{sub 4} described in the previous paper (LixMn2O4) confirmed that the cooperative Jahn-Teller effect (CJTE) from the [Mn{sup 3+}O{sub 6}] octahedra is the mechanism for the cubic to tetragonal phase transformation. The driving force for the CJTE is based upon the electronic structure, therefore changes in electronic structure should lead to changes in the phase behavior. The fact that the LiMn{sub 1.5}Ni{sub 0.5}O{sub 4} does not form tetragonal phase upon discharging (FUJI3, MUCK?), unlike the 100% Mn{sup 4+} spinel Li{sub 4}Mn{sub 5}O{sub 12} (THAC5), led to the hypothesis that an increased degree of covalency as a source for the behavior. An increased covalence would remove the driving force for the transformation, the increased electronic stability achieved in tetragonally-distorted [Mn{sup 3+}O{sub 6}] octahedra, due to a change in electron density and widening of the Mn 3d bands. The STH field is dependent upon the amount of unpaired spin density transferred between the magnetic (transition-metal) and diamagnetic ions through an intermittent oxygen ion, attributable to overlap and electron transfer effects. Therefore, the magnitude of the STH coupling constant reflects the degree of covalency (GESC, HUAN). In the case of LiMn{sub 2-y}Me{sub y}O{sub 4}, the STH coupling constant characterizes the amount of unpaired spin density transferred to the Li{sup +} from the Mn, Co, or Ni. Similarly, the La/Lb ratio of the Mn L-XES is sensitive to the amount of electron density at the Mn site as a higher ratio indicates that the Mn 3d{sub 5/2} level is more populated (GRUS1). An investigation into the effects of Mn-substitution on the electronic structure along with the ramifications to the phase behavior upon changing lithium content was carried out. To accomplish this, a set of LiMn{sub 2-y}Me{sub y}O{sub 4} with Me = Li, Co, or Ni over a range of y were synthesized, characterized, and subjected to changes in lithium content by various techniques.

  20. Investigating the Structure-Property Relationships of Aqueous Self-Assembled Materials

    NASA Astrophysics Data System (ADS)

    Krogstad, Daniel Vincent

    The components of all living organisms are formed through aqueous self-assembly of organic and inorganic materials through physical interactions including hydrophobic, electrostatic, and hydrogen bonding. In this dissertation, these physical interactions were exploited to develop nanostructured materials for a range of applications. Peptide amphiphiles (PAs) self-assemble into varying structures depending on the physical interactions of the peptides and tails. PA aggregation was investigated by cryo-TEM to provide insight on the effects of varying parameters, including the number and length of the lipid tails as well as the number, length, charge, hydrophobicity, and the hydrogen bonding ability of the peptides. It was determined that cylindrical micelles are most commonly formed, and that specific criteria must be met in order to form spherical micelles, nanoribbons, vesicles or less ordered aggregates. Controlling the aggregated structure is necessary for many applications---particularly in therapeutics. Additionally, two-headed PAs were designed to act as a catalyst and template for biomimetic mineralization to control the formation of inorganic nanomaterials. Finally, injectable hydrogels made from ABA triblock copolymers were synthesized with the A blocks being functionalized with either guanidinium or sulfonate groups. These oppositely charged polyelectrolyte endblocks formed complex coacervate domains, which served as physical crosslinks in the hydrogel network. The mechanical properties, the network structure, the nature of the coacervate domain and the kinetics of hydrogel formation were investigated as a function of polymer concentration, salt concentration, pH and stoichiometry with rheometry, SAXS and SANS. It was shown that the mechanical properties of the hydrogels was highly dependent on the structural